This study examined the charge carrier photogeneration and hole transport properties of blends of poly (9-vinylcarbazole) (PVK), $pi$-conjugated polymer, with different weight proportions (0~29.4 wt%) of (PEA)$VOPO_4{cdot}H_2O$ (PEA: phenethylammonium cation), a novel organic-inorganic hybrid material, using IR, UV-Vis, and energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), steady state photocurrent (SSPC) measurement, and atomic force microscopy (AFM). The SSPC measurements showed that the photocurrent of PVK was reduced by approximately three orders of magnitude by the incorporation of a small amount (~12.5 wt%) of (PEA) $VOPO_4{cdot}H_2O$, suggesting that hole transport occurred through the PVK carbazole groups, whereas a reverse trend was observed at high proportions (>12.5 wt%) of (PEA)$VOPO_4{cdot}H_2O$, suggesting that transport occurred via (PEA)$VOPO_4{cdot}H_2O$ molecules. The transition to a trap-controlled hopping mechanism was explained by the difference in ionization potential and electron affinity of the two compounds as well as the formation of charge percolation threshold pathways.