An efficient and concise practical protocol for the synthesis of novel aza-fused polysubstituted pyrido[2 0 ,3 0 :3,4]pyrazolo[1,5-a]pyrimidine derivatives from a readily available aromatic aldehyde, acetophenone and 1H-pyrazolo[3,4-b]pyridin-3-amine in presence of Ba(OH) 2 , under transition metal-free conditions, has been established. This transformation presumably occurs through a sequential Aldol reaction, imine-formation, intramolecular N-cyclization, auto-oxidation sequence of reactions. This protocol, which includes the formation of new C-C and C-N bonds, features a wide substrate scope with a broad range of functional group tolerance.