The synthesis of three push‐pull cationic dyes is reported here together with a photophysical study carried out by stationary and ultrafast spectroscopies. The hyperpolarizability (β) values of the three molecules have been estimated through a simple solvatochromic method based on conventional, low‐cost equipment, which had been tested previously with success in our laboratory. The investigated pyridinium salts showing strong negative solvatochromism bear the same piperidine ring as a strong electron‐donor group and the same thiophenes as electron‐rich π‐linkers, but differ in terms of the N‐substituent on the electron‐acceptor pyridinium unit, namely N‐methyl in compound A, N‐pyrimidin‐2yl in B and N‐2,4‐dinitrophenyl in C. The derived β values were found to increase (in the order A