We present a Kelvin Probe Force Microscopy (KPFM) study on the topography combined with surface potential of hybrid poly(3-hexylthiophene)(P3HT):TiO 2 nanorod materials in dark and under illumination. The hybrid materials with fine and coarse phase separation are displayed. The photo-induced electron accumulation on surface is pronounced under high loading TiO 2 nanorod in the blend. Large surface roughness, large surface height difference and potential variation in the hybrid P3HT:TiO 2 nanorod are present with high content TiO 2 . Additionally, the incorporating a TiO 2 nanorod layer on the surface of hybrid layer to facilitate collecting the electron and blocking the hole is investigated.