Here are some nice campaign changing things you could do with a + 65 Bluff:
Talk Queen Amlaruil and the Elves of Evermeet into allowing the good drow and half-elves to move there permanently.
Talk Waterdeep and all the cities of the Lord's Alliance into joining with Luruar, Aglarond, and Thesk into one grand nation.
Actually unite Thay into a strong, unified nation under one central authority with a strong, unified army.
Convince the Mulhorandi to reclaim the Raurin Desert and all the artifacts in it, and thus reclaiming the glory of Imaskari.
Talking the Grand Caliph of Calimshan into releasing the genies in the Calim Desert, thus reestablishing the Genie Empire of Calimshan.
Convincing Halruaa and Shade into merging into one nation, Netheril reborn.
Convincing the drow of Menzoberranzan they should follow Vhaeruan (or even Eilistraee) and not Lolth.
Convincing Menzoberranzan to ally with Luruar, and vice versa.
Convincing an entire land to convert to one, and only one, religion.
Convincing dwarves to live with elves, and vice versa (and halflings, with both.)
Convincing Luruar and King Obold of the Orcs to unite.
Convincing the orcs to turn away from Grummsh.
Convincing Rashemen to ally with Thay.
Convincing the Hordelanders to ally with any western country.
Convincing the Sha'ir of Zakhara to share all their magical secrets with the Northerners.
Convincing the Heralds to share all their secret lore with one country.
Convincing the Sages of Candlekeep to share all their secret lore with one country.
Convincing Iuz that an alliance with Furyondy and Veluna would be useful against Greater Ahlissa.
Convincing Keoland and the Scarlet Brotherhood to ally and take over all the neighboring lands (and the Lortmils.)
Convincing Greater Ahlissa and North Kingdom to ally with Nyrond and Iuz to invade the western lands and reestablish the ancient glory of Aerdi.
Convincing the Scarlet Brotherhood that slavery is wrong, and all the slaves must be released at once.
Convincing the Baklunish to reunify into a new Baklunish Empire.
Convincing the drow to come to the surface for good.
Convincing the elves that life underground would suit them perfectly.
Talking the current holder of the Hand and Eye of Vecna into giving those items to you.
Convincing everyone that kender are really ok, and should be treated with all honor and respect. Which would include knighthoods, mage training, and positions of leadership in Solamnia, Thorbardin, Mithas, and other places.
Convincing the Knights of Solamnia to ally with the Knights of Neraka to conquer the draconians.
Convincing the minotaurs to ally with the elves to conquer the Knights of Neraka.
Convincing the Knights of Steel to ally with the Knights of Neraka to conquer the Knights of Solamnia.
Convincing any country to accept all the latest gnomish inventions from Mount Nevermind, and put them to immediate use.
Convincing the ogres to make permanent alliance and peace with the dwarves.
Those are some good starters.