Covalent organic frameworks (COFs) as an attractive metal-free heterogeneous photocatalysts have become a powerful platform. This work, we designed and got a novel dual-pore COF, anthraquinone-porphyrin-based two-dimensional (2D) COF, AQ-Por-COF, in which the porphyrin amine (Por-NH2) and anthraquinone bridging aldehyde (AQ-CHO) were introduced into the structure. AQ-Por-COF was characterized using FT-IR, PXRD, UV-vis light adsorption spectra, TGA, SEM and XPS. In addition, the photocatalytic performances and stability of AQ-Por-COF was appraised with the light-induced selective oxidation of amines. The photooxidation reactions attained high conversions and produced aldehydes having predictable selectivities with ambient air as the oxidant under optimal conditions. And the activities of light LEDs was found to be lying in the following order: blue > purple > white > red. The experiments also indicated that the conjugation of Por-NH2 and AQ-CHO is necessary for the enhanced catalytic activity. Furthermore, AQ-Por-COF displayed strong photo-response abilities and suitable photocatalysis potentials, enabling the activation of O2 to superoxide anions (O2•−), the main active oxygen species, which was generated from the activation of oxygen by the separated photogenerated electrons under light irradiation. Finally, the results demonstrated that the insoluble photocatalyst, AQ-Por-COF, exhibited excellent photocatalytic activity, high selective, good recyclability and reusability.