A highly efficient heterogeneous nanocatalyst based on modified poly (styrene-altmaleic anhydride) (MPSAMA) in three steps was fabricated. Then, the MPSAMA surface was modified using chlorosulfonic acid (CAS) to achieve a sulfonated MPSAMA (SMPSAMA) with high acidity and efficiency. FT-IR spectroscopy, CHNS analysis, FESEM, and TGA were employed to characterize the prepared nanocatalyst. The catalytic activity of the SMPSAMA was examined for the formation of the polyhydroquinoline derivatives through Hantzsch condensation and the synthesis of 2-amino-4H-chromene derivatives. This new heterogeneous nanocatalyst has been efficiently used for the synthesis of bifunctional bis polyhydroquinoline, and new alkylene bridging bis 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-benzo[b]pyran derivatives.