Hollow microporous organic networks were prepared by using silica spheres as the template and tris(4-ethynylphenyl)amine and 2,6-diiodo-9,10-anthraquinone as the building blocks for the Sonogashira coupling. The resultant materials bearing triphenylamine and anthraquinone moieties showed efficient visible light absorption and catalytic activities in the photochemical oxidative coupling of benzylamines. Through the comparison studies of hollow and nonhollow catalytic materials, the diffusion pathway effect of the substrates was clearly observed in the photochemical conversion of benzylamines.