Perovskite (PVK) films deposited directly on n-type crystalline Si substrates were investigated by two operating modes of the surface photovoltage (SPV) method: i) the metal-insulator-semiconductor (MIS) mode and ii) the Kelvin probe force microscopy (KPFM). By scanning from 900 to 600 nm in the MIS mode we consecutively studied the relatively fast processes of carrier generation, transport, and recombination first in Si, then on both sides of the PVK/Si interface, and finally in the PVK layer and its surface. The PVK optical absorption edge was observed in the range of 1.611.65 eV in good agreement with the bandgap of 1.63 eV found from photoluminescence spectra. Both SPV methods evidenced an upward energy band bending at the PVK/n-Si interface generating positive SPV. Drift-diffusion modeling allowed us to analyze the shape of the wavelength dependence of the SPV. It was also observed that the intense illumination in the KPFM measurements induces the creation and migration of negative ions and their trapping at the surface leading eventually to an overall negative SPV transient. Finally, ageing effects were studied by measuring again SPV spectra after one-year storage in air, and an increase in the concentration of shallow defect states at the PVK/n-Si interface was found.