A series of new polymers containing porphyrin, poly(p-phenylenevinylene) (PPV), and/or a pendant fullerene unit has been synthesized. The cyclic voltammetry showed us a good candidate for a photoinduced electron-transfer system. More important, the photocurrent measurement revealed an interesting phenomenon that the photocurrent increased with the contents of the fullerene in the polymers increased. SEM images displayed the aggregation superstructures of three polymers. Nanobriquetting, nanofiber, and hierarchical porous structure were observed, respectively. The results indicated that the axial coordination of metal porphyrin and Bipy was very important to control the aggregation morphologies of the polymers.