First-principle calculations were conducted on porous graphene structures to compare the properties of a pol-yphenylene super-honeycomb network (PSN) with those of an oxygen-terminated PSN (O-PSN) obtained from oxygen substitution. The band structures, densities of states, and simulated STM images were presented along with the infrared and Raman spectra, which could distinguish the properties of O-PSN from PSN. Moreover, the work functions of PSN and O-PSN were found to be ~1 eV higher than that of perfect graphene. Furthermore, our results showed that the two oxygen atoms replacing the hydrogen atoms tend to be separated as far as possible at the PSN pores.