By means of distillation precipitation polymerization,the silica-hybrid particles with polyazobenzene shell (PAzo@SiO2) microspheres were prepared with 6-(4-methoxy-4’-oxy-azobenzene) hexyl methacrylate (Azo-M) as monomer,divinylbenzene (DVB) as cross-linker,and ～250 nm vinylated sol-gel silica particles as template. Hollow polyazobenzene microspheres were further developed after selective removal of the silica cores with HF solution. When the content of DVB related to Azo-M is 20 wt%,the acetonitrile is 200 mL,and the polymerization time is 4.5 h,the hollow PAzo microspheres with about 20 nm shell are successfully fabricated. These hollow PAzo microspheres have excellent reversible photoisomerization,and their first-order rate constant of trans-cis isomerization only decreases 11.8% compared with homopolymer of azobenzene (Homo-PAzo). By means of distillation precipitation polymerization, the silica-hybrid particles with polyazobenzene shell (PAzo @ SiO2) microspheres were prepared with 6- (4-methoxy-4’-oxy- azobenzene) hexyl methacrylate DVB) as cross-linker, and ~ 250 nm vinylated sol-gel silica particles as template. Hollow polyazobenzene microspheres were further developed after selective removal of the silica cores with HF solution. When the content of DVB related to Azo- % of the acetonitrile is 200 mL and the polymerization time is 4.5 h, the hollow PAzo microspheres with about 20 nm shell are successfully fabricated. These hollow PAzo microspheres have excellent reversible photoisomerization, and their first-order rate constant of trans-cis isomerization only decreases 11.8% compared with homopolymer of azobenzene (Homo-PAzo).