In this work, the P3HT:PCBM:pentacene (1:0.8:0.065 by weight) inverted polymer solar cells with roughened Aldoped ZnO (AZO) nanorod array were fabricated. The pentacene doping could modulate the hole mobility and the electron mobility in the active layer. The optimal hole-electron mobility balance (μh/μe=1.000) was achieved as the pentacene doping ratio of 0.065. The 100-nm-long AZO nanorod array were formed as the carrier collection layer and the carrier transportation layer of the inverted polymer solar cells using the combination techniques of the laser interference photolithography method and the wet etching process. Because the AZO nanorod array was prepared using the wet etching process, more defects were formed on the sidewall surface of the AZO nanorods. In this work, the photoelectrochemical (PEC) method was used to grow Zn(OH)2 and Al(OH)3 thin layer on the sidewall surface of the AZO nanorods, which could reduce the carrier recombination path in the inverted polymer solar cells. Compared with the P3HT:PCBM:pentacene (1:0.8:0.065) inverted polymer solar cells without PEC treatment, the short circuit current density and the power conversion efficiency of the inverted polymer solar cells with PEC treatment were increased from 14.56 mA/cm2 to 15.85 mA/cm2 and from 5.45% to 6.13%, respectively. The enhancement in the performance of the inverted polymer solar cells with PEC treatment could be attributed to that the PEC treatment could effectively passivate the defects on the surface of the AZO nonorods.