I had two friends playing an incubus and a succubus couple. The incubus went for grapple monster and looked for anything to increase his number of natural attacks (fanged mask (or was it fanged ring?), horned helmet, some other things, iirc) or his size/strength for grappling. He went into Warshaper and had some Barbarian for pounce (Lion Totem variant from C.Champion).
The succubus was more rogue and sorcerer oriented and maxed the hell out of her charisma. Her main "attack" was a wand of Whirling Blade, a level 2 spell from spell compendium to attack every creature in a 60 ft line with a slashing melee weapon. Except you use your charisma for attack and damage. She had a +12 charisma bonus (I think she was also a half vampire

), so a line attack with that was actually quite devastating.
Look for the +X to Y thread, there are a LOT of means of adding charisma to things. A marshal dip for charisma to all dex-based checks (which includes initiative) for yourself and all allies within 60 ft rocks, for example.
EDIT: I always liked Stunning Surge from Magic Item Compendium for high charisma characters. It's a +1 weapon property that can be used
1 + charisma modifier times per day as a swift action after you hit with a melee attack. The target must make a fort save or be stunned for 1 round. The save DC is 10 + 1/2 your level (HD) + charisma modifier.