We report on photoinduced inverse spin-Hall effect (ISHE) measurements as a function of the incident photon energy in the 4–50 K temperature range for a Pt/n-doped Si junction. Optical spin injection allows generating a spin-oriented population of electrons and holes around the Δ valleys and Γ point of the Si Brillouin zone, respectively. Spin-polarized carriers cross the Pt/Si contact and then enter the Pt overlayer, where spin-to-charge conversion occurs by means of spin-dependent scattering with Pt nuclei. For temperatures T up to 20 K, most of the dopants are not ionized, so that the electric field, stemming from the contact potential between Pt and Si, extends to the whole Si substrate, which becomes insulating, and only spin-oriented holes reach the Pt layer and contribute to the ISHE spectra. For T>20 K, donors are partially ionized, and the resulting space charge close to the Pt/Si interface leads to the formation of a Schottky contact where the electric field rapidly vanishes within a few micrometers. As a consequence, also spin-polarized electrons enter Pt by means of thermionic emission, contributing to the ISHE signal. We numerically solve the one-dimensional spin drift-diffusion equations for holes and electrons and estimate the temperature dependence of the spin lifetime in Si for both populations, demonstrating that Si may serve as a versatile platform for spintronic applications, able to leverage both electrons and holes.