Tin dioxide (SnO2) nanoparticles efficiently catalyzed unsymmetrical four‐component Hantzsch condensations of various aldehydes, dimedone, ethyl acetoacetate, and ammonium acetate to form polyhydroquinoline derivatives in excellent yields. This novel method offers several advantages over the traditional method of synthesizing these compounds, including safety, mild conditions, short reaction times, high yields, and an easy workup.