NOTE: This method can also be used to earn an S Rank for a 2-for-1 deal.
For this achievement you'll have to earned an A Rank for Bet the Future Boss Battle between the 5 Kages and Madara Uchiha.
For FACTORS on reaching high Rank for Boss/Pseudo battles please consult with this trophy solution:
There will be several part to this EPIC Boss Battle but you'll only be getting 1 rank.
The first part of this battle will be Tsunade (Gaara, Raikage as supports) against Madara. You'll be engaging normally, as you lower his health until a cutscene ensues. To which the scene will take to the skies as Madara displays his overwhelming power.
The second part of the battle will be Tsunade (Mizukage, Raikage as supports) against Madara. Here you'll need to use the Raikage effectively to get Madara off of the high ground, damaging him in the process.
The third part of the battle will be Tsunade (Tsuchikage, Raikage as support) against Madara. This battle proceed just as the last, but with Madara changing the scene to cause environmental damage, also performing crushing combos and wide-range attacks. He will also be in his Awakened State so more damage and easier guard breaks are to be of concern.
After you've dealt enough damage to Madara a cutscene will ensue and trigger the 4th part of the battle. The entire battlefield will be swept and you'll take to the skies as you battle Madara's Susanoo form. Here you'll choose an Ultimate Decision to fight as a unit, or use all of your power alone. This battle with Susanoo will consist of utilizing your support actions when you've opened a point to attack. After which Susanoo will form totem shields. You'll need to destroy these in order to re-open a point of entry for attack, as well as be wary of Madara's Fire Jutsu, Susanoo's wide-range sword attacks, and Madara's Meteor showers.
Once you've gotten Madara's health to very low red, a cinematic IA will commence. Input the on-screen button commands to finish off the battle.
If, for any reason, you aren't able to earn an A Rank no worry. You can retry ANY battles post-story in the Ninja World timeline for another try.