This achievement is obviously for completing all story missions.
This achievement for most people will pop when obtaining 100% completion in Smuggling, Security, Influence and Production and completing the 2 missions for the final boss and the 2 DEA missions.
Note: This achievement is currently known to be buggy/glitchy for no apparent reason.
I had completed all story missions and had 100% in all operations, but my achievement tracker was on 99%. At this point in time, no one really can pin point what makes this occur, but there is a solution that worked for me.
What worked for me to pop this achievement was to go into each provence and hit
to bring up the option to replay the missions. Now what I did was selected to replay a mission and waited for the mission checkpoint message to pop up on my screen. Once that happened I simply went back into the replay mission option and selected the next one on the list and continued to do so for the rest of the provence before moving onto the next one and repeated the process moving around the map.
For me, my achievement popped using this method in about the 4th provence I tried this method on.
Hopefully this method will work people that are stuck on 99% progress on the achievement tracker.
The Peruvian DLC missions do not count toward overall progress on the tracker.
Credit to Karlos Fantano on the ubisoft forums for the solution which helped me unlock my achievement.
EDIT: This achievement has also been unlocking for a number of people when Narco Road DLC is started