A new conjugated polymer PPV-PCN containing alternating alkoxy-substituted aromatic and cyano-substituted aromatic units was synthesized and characterized by NMR, FIR, GPC and TGA. The UV-vis absorption spectra and photoluminescence emission spectra in solution/films were characterized. The results indicate PPV-PCN has a smaller optical band gap value (2.05 eV) compared to homopolymer MEH-PPV, it is ascribed to PPV-PCN with structure of alternative electron-rich alkoxy substituted aromatic and electron-deficient cyano group along conjugated backbone. Its photoinduced charge transfer application in trinitrotoluene (TNT) detection was studied, and the results show that this polymer can be a potential material for detecting TNT in solution. Two types of cells, including inverted-type and conventional-type were studied for PSCs application as well, and the results indicate that the inverted-type device demonstrates better long-term ambient stability as compared to the conventional device and achieves 0.91 % power conversion efficiency finally.