Defective or heteroatom-doped metal-free carbon materials (MFCMs) have been regarded as efficient oxygen reduction reaction (ORR) catalysts in the past decade. However, the active centers for ORR in MFCMs are hard to confirm precisely and synthesize controllably through common methods such as high-temperature pyrolysis or heteroatom doping. To verify the precise structure acting as the active center for the ORR, we first report two crystalline metal-free thiophene-sulfur covalent organic frameworks (MFTS-COFs) as ORR catalysts. The MFTS-COFs show more positive catalytic capability than the thiophene-free COF, indicating that pentacyclic thiophene-sulfur building blocks act as active centers to induce ORR catalytic activity. MFTS-COFs with higher contents of thiophene-sulfur exhibit better ORR performance. The experimental identification is supported by density functional theory calculations. These results thus demonstrate that rational design and precise synthesis of metal-free crystalline organic materials can promote the development of new ORR catalysts.