Organic - inorganic nanostructured hybrids based on N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,l'-biphenyl)-4,4'-diamine (MTPD) and anatase TiO2 were prepared via layer-by-layer deposition method. The MTPD/TiO2 hybrids were characterized by UV - Vis absorption spectra, photoconductivity measurements, and surface photovoltage spectra (SPS). Due to the change of the aggregated structure caused by the addition of TiO2, MTPD showed blue-shifted absorption spectrum. The photosensitivity of MTPD/TiO2 nanostructured hybrids was increased by two times when compared with that of its single component. Studies on the SPS revealed that the efficient light-induced charge separation and transfer between MTPD and TiO2 was responsible for the improved photosensitivity. The MTPD/TiO2 hybrids exhibited high photosensitivity to ultraviolet light with weak intensity and acceptable stability under ultraviolet radiation, which endow the hybrids potential applications in the field of ultraviolet photodetection.