Using Kelvin probe force microscopy (KPFM) and temperature-dependent current-voltage characteristics, we study the charge transport across an n-TiO2/p-Si heterojunction. In particular, the KPFM result shows a variation in the work function at the TiO2 surface. On the other hand, temperature-dependent current voltage characteristics depict a non-ideal hole-blocking behaviour of the same. In addition, the measured barrier height is found to decrease with temperature and does not follow the thermionic emission theory, strongly suggesting an inhomogeneous nature of the barrier. The observed barrier inhomogeneity is attributed to the nanoscale height modulation, arising due to the growth dynamics of TiO2 and corroborates well with the KPFM map. The presented results will open a new avenue to understand the charge transport in TiO2-based nanoscale devices. (C) 2017 Elsevier B.V. All rights reserved.