A photoconductivity (PC) study in as deposited porous silicon (PS) thin films is presented in this work. PS thin films were produced by the electrochemical anodizing method at different anodizing times. The films surfaces were characterized by SEM and porosity was determined by gravimetric methods. Photoluminescence and PC measurements were taken at room temperature. The maximum of the photoluminescence spectra are located around 650 nm, whereas those of PC are placed around 400 nm. The maximum of the photoluminescence signal shifts toward short wavelengths as the quantum dimension of the material skeleton diminishes, while any spectral displacement of the photocurrent signal as the porosity of the material increases is not observed. The spectral position of the PC signal does not change because it is strongly affected by the large quantity of defects present in the sample surface which diminishes the mean free path of the carriers to reach the electrodes. In all the samples photocurrent is small around 10−1 μA and the intensity of the signal goes down as the porosity increases. Two mechanisms exist that compete with one another, the carrier generation and recombination through light emission centers which diminish the photocurrent.