Two three-dimensional (3D) network polymers (1 and 2), in which zinc(II) or cobalt(II) phthalocyanines were interconnected with twisted 9,9'-spirobifluorene linkers, were synthesized in order to investigate their performance as heterogeneous catalysts for thiol oxidations. From the spectroscopic analyses of two dimers (3 and 4) as component units of the network polymers, 3 connected with a short linker revealed electronic interaction between the two phthalocyanine units. Micrometer-sized polymer particles were formed due to the condensation of the twisted 9,9'-spirobifluorene linkers in the presence of zinc or cobalt ions. The dispersed solutions of 1 and 2 had sharp Q-bands, indicating the prevention of stacking among phthalocyanine moieties within the polymers. Powdered X-ray diffraction pattern and N-2 adsorption-desorption analyses suggested that 1 created small and rigid cavities as compared with 2 through the regular spatially arrangement of the phthalocyanine moieties in the 3D networks. The photocatalytic and catalytic activities of 1 and 2 for thiol oxidations using molecular oxygen were examined. We found that the catalytic activity of 1 was higher than that of 2 having larger cavities.