We investigated the photovoltaic properties of multilayered devices consisting of ITO/oxide/Tetraphenyl porphyrin (H2TPP)/Fullerene (C60)/Bathocuproine (BCP)/Al structures. The VOC markedly increases with the insertion of NiO and MoO3 hole collection layers. However, the "kink" behaviors and temperature dependent properties are observed for the devices with and without MoO3 especially for the thick H2TPP film. We demonstrated the analysis of the photovoltaic properties using the Poole-Frenkel and Schottky models based on the dielectric behaviors of porphyrin and MoO3 layers.