The Face Beneath (Caspar/Mercie), I love how bittersweet it is with the ending and it made me like Caspar, not to mention the rewards are great and I love the map as well.
Some honorable mentions would be Darkness Beneath the Earth for some of the same reasons above and just because listening to Hubert's voice is always a bonus, Silver Maiden
and Weathervanes of Fódlan just because I love exploring more of the relation between Gilbert and Annette.