Here is the full list of all 71 Napoleon: Total War achievements.
Have a 100% approval rating
Win ten SP Campaign naval battles
Win any campaign without a single autoresolve
Make all major nations like you (very friendly)
As Britain, ensure that all regions in Spain are liberated back to Spanish control
Win Europe Campaign in medium within historic time
Win 10 decisive victories
Win a match with only first rates
Play a MP naval battle with every faction
Board 5 ships in a single battle
Win 6 MP Naval Battles in a row
Win a match without any ships of the line
Win 50MP Land Battles
Win 10 MP Land Battles in a row
Play a MP land battle with every faction
Win a match without any infantry
Win a battle using only Light Infantry and Artillery
Win Italian Campaign in hard
Start any campaign, battle or historical battle
Capture 10 regions
100000 soldiers die in battles with you, friend and foe
Win 15 SP Campaign land battles
Have 10 protectorates at one time
Play a MP Campaign
Win any campaign by auto-resolving battles
Conquer all of Europe
Win the Peninsular Campaign as France
As France, attain over 50% pro-French sentiment in 10 of your regions
Gain 8000 per turn in trade revenue
Win Europe Campaign in easy
Win 10 pistol duels
Win Egypt Campaign in easy
Win a match against someone with double your skill rating
Declare war on all nations the first turn, never negotiate peace, and win the game
Win a MP naval battle
Take other player's capital within 20 turns
Win 10 land battles
Win a match against a player with double your skill rating
Win Egypt Campaign in hard
Win the Peninsular Campaign as Britain
Win the Peninsular Campaign as Spain
Win 10 sword duels
Capture a region in the Peninsular Campaign
Assassinate 15 people
Cover 50,000 sea or land miles with your armies and fleets
Have 6 allies simultaneously
Play the game for 50 hours total
Win Italian Campaign in easy
Win Egypt Campaign in medium within historic time
Play the game for 30 hours total
Win Italian Campaign in medium within historic time
Play the game for 10 hours total
Win a match having spent half as many funds as your opponent
Play a historical land battle
Win Europe Campaign in hard
Have three generals with full skill level in one campaign
Win Silver in 5 Historic Battles
Win Gold in all Historic Battles
Play 100 multiplayer naval battes
Win a MP Italian Campaign as France
Win a MP Italian Campaign as Austria
Win a MP Egypt Campaign as France
Win Egypt Campaign as Ottomans
Win European MP Campaign as France
Win Europe Campaign as Russia
Win Europe Campaign as Austria
Win Europe Campaign as Prussia
Win Europe Campaign as England
Other player's faction is last to die
Win campaign having given enemy player 50000 gold
Start the Peninsular Campaign in multiplayer