Series of azobenzene-bridged pillar[5]arene-based [3]rotaxanes with different alkyl chain length of guest molecules were constructed by threading-endcapping method with alkylenetriazole as axile and tetrahydrochromene as endcapping group. The encapsulation of pillar[5]arenes were proved by high-resolution mass, 1H NMR and NOESY spectra. The photo-responsive property were examined by irradiation of the synthesized [3]rotaxanes with 365 nm and blue light LED, which caused trans to cis and cis to trans isomerization, respectively. Irradiation of corresponding model guest compounds without pillar[5]arene encapsulation resulted in near completely trans to cis and cis to trans isomerization, indicating the existence of pillar[5]arenes is the determining factor for the comprised photo isomerization efficiency.