A facile one-pot method is reported for the synthesis of 4-alkoxy-2-aminothiophene-3- carbonitriles. Transesterification of trimethylorthoacetate technique allowed introducing alkoxy substituents into 2-aminothiophene ring system. Diverse alkoxy substituents could be introduced efficiently by using this methodology. Further the synthesis of some of new 4- alkylamino-2-aminothiophenes is also reported.