In this article, the synthesis of a two-dimensional sulfone-based microporous COF, Ni-P has been executed via C-S coupling of nickel (II) tetra(p-bromophenyl) porphyrin with sulfur powder in the presence of the catalytic amount of CuI and benzotriazole in an inert atmosphere (N2) at 120 °C for 7–8 hrs. The authenticity as well as physiochemical properties of the compound have been investigated using FT-IR, XPS, XRD, TGA, SEM, and BET. The optical band gap (1.9 eV) and electrochemical band gap (2.1 eV) of Ni-P have been calculated through UV–vis and cyclic voltammetric study which finds Ni-P a suitable candidate for photocatalytic study. In the chemical transformation reactions, Ni-P shows an excellent conversion rate of benzylamine for the generation of N-benzylidene benzylamine through oxidative coupling (yield ∼ 99 %). In the photostability study, even after 5 times, it shows good recyclability as evidenced by FT-IR and XRD data.