Two covalent organic framework (COF) films supported by a glass substrate were obtained by solvothermal reaction of an electron donor with electron acceptor 1,3,5-triformylbenzene (TF) or 2,4,6-triformylphloroglucinol (TFP), respectively. The TFP-BD film exhibits a nonlinear absorption coefficient of -3.01 × 105 cm GW-1. The TFP-BD film can aggregate electrons around the connected monomer through the D-A effect due to its highly polar and electronegative carbonyl oxygen atoms, thereby modulating the electronic structure of the COFs. This work provides a novel approach for the structural modulation of optical materials with strong nonlinearity.