The trans and cis forms of N-alkyl-4-styrylpyridinium derivatives (CnSP: n= 4, 8, 12, 16) were successfully synthesized and purified. The derivatives of styrylpyridinium cause photoisomerization when they are illuminated with UV light. The pressure-area isotherms of CnSP and their derivatives were studied to reveal the effect of alkyl chain length. The photoisomerization of CnSP monolayers at the air/water interfaces was indirectly studied by measuring surface tension changes with photoirradiation on the water surface. The characteristics of CnSP were furthermore studied with UV-vis, surface pressure-area isotherms, surface potential-area isotherms, Brewster Angle Microscopy (BAM) at the air/water interface, and optical diffraction efficiency on the ultrathin films.