We report the increase in open-circuit voltage (V oc ) by inserting of MoO3 layer on ITO substrate to improve built-in potential of organic solar cells (OSCs). In the OSCs using 5,10,15,20-tetraphenylporphyrine (H2TPP) as a p-type material and C60 as a n-type material, the Voc effectively increased from 0.57 to 0.97 V as increasing MoO3 thickness. The obtained highest V oc (0.97 V) is consistent with the theoretical value estimated from the energy difference between the LUMO (−4.50 eV) of C60 and the HOMO (−5.50 eV) of H2TPP layer. Importantly, the enhancement in the V oc was achieved without affecting the short-circuit current density (J sc ) and the fill-factor (FF). Thus, the power conversion efficiency of the device linearly increased from 1.24% to 1.88%. We also demonstrated that a MoO3 buffer layer enhances the stability of OSCs after photo-irradiation. We have investigated the stability of OSCs using H2TPP and N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine as a p-type layer. The both devices with MoO3 layer showed improved stability. These results clearly suggest that the interface at ITO/p-type layer affects the device stability.