Through story progression this achievement can be earned.
From the start of Chapter 1: Rescue the Kazekage, besides special events, missions, requests, ect. these are the battles you'll partake in for the chapter.
Gaara vs Deidara (Boss Battle- S Rank)
Neji vs Kisame
Might Guy vs Kisame
Kakashi vs Itachi
Tenten vs Neji
Rock Lee vs Might Guy
Sakura (Chiyo as Support) vs Sasori (Boss Battle- S Rank)
Naruto vs Deidara
After your battle with Deidara you'll complete Chapter 1: Rescue the Kazekage and earn 5G!