You get it by having 100 consecutive wins in the Battle Tower.
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the first star is easy (beat the elite four and champion)the next star can be obtained 4 ways:Winning any Master Rank Super ContestEarn a Platinum Flag in the Underground by getting 50 flag capturesCollect all 493 Pokemon in the national dexDefeat 100 Trainers in a row in the Battle Tower
All It Does Is Add One star To Your Trainer Card