Abstract A facile conversion of 6‐(2‐arylidenehydrazineyl) purines to [1,2,4] triazolo [3,4‐i] purines is presented using PhI(OAc) 2 as oxidant in only 10 min under room temperature. This approach is metal‐free, wide functional group tolerant, and provides an efficient and convenient method to synthesize purine‐fused tricyclics.