An efficient synthesis of novel benzo[f]Chromeno[2,3‐d]pyrimidine and unknown benzo[f]chromeno[2,3‐d][1,2,4]triazolopyrimidine derivatives is described utilizing ethyl‐2‐amino‐4‐phenyl‐4H‐benzo[f]chromene‐3‐carboxylate as precursor via aza‐Wittig reaction. The process proved to be simple, high‐yielding, and efficient.