The homogenous catalytic system “FeCl3/PVP” and green solvent system “water/PEG‐400” has been presented as a green pathway to synthesize 4‐amino‐1‐aryl‐1H‐pyrazole‐4‐carbonitrile and its derivatives from a series of phenyl hydrazines and malononitriles. The new approach enhanced the reaction yield of the desired product up to 97% in 2–4 h time whereas the traditional thermal method gives only 87% maximum yield in relatively longer reaction time (3‐7 h). The catalytic system has remarkable benefits such as it is inexpensive, stable, easy to prepare and very efficient with a small loading of FeCl3 (5 mol%).