Benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) is a porous organic material with a conjugated backbone, highly dispersed π-π conjugation, and stabilized chemical bonding, which has the ability to act as a visible light photocatalyst. Starting from BTT, two porous organic materials linked to ethylene and imine were synthesized respectively with 1,4-phenylenediacetonitrile (PDAN) and 1,4-phenylenediamine (PDA) structural units. The less reversible ethylene can only form conjugated microporous polymers (CMPs), i.e., BTT-PDAN-CMP, while on the contrary, the more reversible imine can build covalent organic frameworks (COFs), i.e., BTT-PDA-COF.Although BTT-PDAN-CMP is amorphous, it shows better photovoltaic properties than BTT-PDA-COF, due to the enhanced electron transfer from ethylene. better photoelectric properties. BTT-PDAN-CMP proved to be an efficient photocatalyst. In fact, BTT-PDAN-CMP, as a visible light photocatalyst, showed higher efficiency than BTT-PDA-COF in selective aerobic sulfur oxidation. Driven by green light on BTT-PDAN-CMP, molecular oxygen was converted into superoxide and single-linear state oxygen, which contributed to the highly selective formation of organic sulfur oxides.