KrazyGlue
Smash Champion
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#242 Blissey
Type- Normal
Ability #1- Natural Cure: The pokemon's stats effect is removed when i is withdrawn from battle.
Ability #2- Serene Grace: The chances of a move's effect happening double.
Base stats- 255 HP/10 ATK/10 DEF/75 SP.ATK/135 SP.DEF/55 Speed
Arometherapist
Blissey @ Leftovers
Natural Cure: Calm/Bold
252 HP/252 defense/4 special defense
Aromatherapy
Wish/Softboiled
Toxic/Thunder Wave
Seismic Toss/Flamethrower/Ice beam
Pretty much the most standard set for blissey. This gives it a whopping 714 HP and a somewhat passable 130 defense. It really doesn't need much special defense because its base stat is amazing. A great special wall and team supporter. Your choices for the last three moves depend on whether you want your blissey to focus more on self-support or team support. For self-support, use Softboiled and toxic; for team support use wish, thunder wave, and flamethrower/Ice beam (whichever you need more).
Counter Blissey
Blissey @ leftovers
Natural Cure: Bold
252 HP/252 defense/4 special defense
Counter
Wish
Toxic/Thunder Wave/Protect
Seismic Toss/Flamethrower
My favorite set. If you're hit for 40% one turn, counter next turn for a OHKO. Same stats as above. As you can see, it's similar to the first set, but has a somewhat different strategy.
Offensive(ish) Blissey
Blissey @ leftovers
Natural Cure: Calm/Bold
4 HP/252 defense/252 special attack
Ice Beam
Flamethrower/Thunderbolt
Softboiled
Calm Mind
A set used less and less now, but still somewhat viable to surprise flygons and salamences, plus flamethrower is blissey's only way to deal with steel types. Thunderbolt gets some bulky water coverage, but is generally inferior to flamethrower.
Extra options:
A choice specs set is also useable, but blissey is not really a sweeper and loses some of its effectiveness without softboiled. Chople Berry is a viable substitute for leftovers on most sets.*
Serene Grace can work with the special attacking sets, but generally Blissey is more comfortable with the free stat healing of Natural Cure.
Shadow Ball hits those pesky ghosts who sometimes carry substitute. If they do, they can ignore toxic, thunder wave, seismic toss, and counter. So shadow ball is considerable. Speaking of special attacks, grass knot, HP fighting, and HP ground are all viable options for the offensive set; it really depends on what kind of coverage you are looking for.
Sing causes the extremely irritating sleep condition. But its terrible accuracy (55) can be very frustrating. And you thought hypnosis had bad accuracy. Still, if it works, you're in command.
Blissey also has some setup options with sandstorm, stealth rock, light screen, and gravity.
Safeguard protects you from status effects for awhile, allowing you to keep blissey out longer. However, you could probably make do without it between the support of natural cure and aromatherapy. Heal bell is the same as aromatherapy, but pokemon with the soundproof ability are uneffected by it, therefore there's not much of a point for heal bell.
Sweet kiss causes confusion with 75 accuracy, but it's not the best use of one of blissey's move slots.
Charm sharply lowers the attack of the other pokemon, making it hellish to defeat blissey. Unfortunately, the opponent will often be able to find a good time to switch in when you're not using charm and then outspeed you, making charm heavily reliant on prediction.
Psych up is great against other defensive walls. Psych up against an iron defense and you're in a great position. Unfortunately, after one use this becomes too predictable, and this is useless against a swords/dragon dancer. Defense curl raises defense one level but has many of the same issues as psych up. In addition, it only raises defense one level at a time, putting blissey's support skills on hold.
EVs:
Should be going in to HP and defense, unless you're using the special attack set.
Troublesome pokemon:
Pretty much anything with a good fighting move. Some common examples: Machamp, Infernape, and Lucario. And there's plenty more where that came from.
Unless you're using a special attacker, taunt is a major issue. If someone uses trick on you, blissey could end up with a choice item, rendering it near-useless.
Ghosts with substitute, as I said, ignore toxic, thunder wave, seismic toss, and counter. Gengar is unaffected by the above (except Twave) even without a sub, and sometimes carries focus blast.
If you don't have flamethrower: Metagross and Scizor scare off blissey because it has no way of getting rid of them without dying. Scizor often tosses in a couple of swords dances, so it's best to switch away before he sets himself up to devour your team. In fact, pretty much any steel type can do whatever setup it wants against blissey. This is why flamethrower is a good option.
Dragon/Swords dancers scare off blissey and gain sweeping potential while you switch away.
*
Thank you to Cost for suggesting this.