Toward visible light photocatalysis, covalent organic frameworks (COFs) have recently garnered growing attention. The effect of different orientations of imine of imine-linked COFs on photocatalysis should be elucidated. Here, two COFs are developed with 2,5-diphenylthieno[3,2-]thiophene (DPTT) and 1,3,6,8-tetraphenylpyrene (Py) linked by imine, affording DPTT-Py-COF and Py-DPTT-COF, respectively. Distinctly, DPTT-Py-COF and Py-DPTT-COF have high crystallinity and porosity, paving the way to highly efficient photocatalysis. Theoretical calculations demonstrate that both DPTT-Py-COF and Py-DPTT-COF are of similar bandgaps but of varied energy positions due to the different orientations of imine. Besides, characterizations disclose that DPTT-Py-COF delivers more enhanced charge separation and transfer than Py-DPTT-COF. Probed by the oxidation of amine to imine, DPTT-Py-COF exhibits a blue light photocatalytic performance superior to that of Py-DPTT-COF. DPTT-Py-COF, a highly recyclable photocatalyst, enables the oxidation of various amines to imines with oxygen. This work highlights that tuning the microenvironment of COFs unravels tenable performances in photocatalysis.