In this contribution, the polymer poly(2‐methoxy‐5(2′‐ethyl‐hexyloxy)‐1,4‐phenylene vinylene) (MEH‐PPV) is researched at the aspect of electronic and structural properties to locate the relationships between structures and the experimental properties by employing DFT and TD‐DFT method. The studied properties refer to the geometry features, absorption spectra, frontier molecular orbital properties, hole transport properties, and exciton dissociation ability at polymer/PC61BM interface. In addition, four MEH‐PPV derivatives, MEH‐PPV substituted with F atoms, are designed and studied through comparing with the properties of MEH‐PPV. The results indicate that MEH‐PPV has low HOMO levels and large hole transport property, which result in its preferable performance. Besides, the designed polymers are promising candidates as PSC donors due to better exciton dissociation ability and larger theoretical VOC owing to lower highest occupied molecule levels, in special, MEH‐PPV‐Fc has better hole transport properties than MEH‐PPV due to smaller m*.