Temperature-dependent studies of the electrical and optical properties of cross-linked PbS nanocrystal (NC) solar cells can provide deeper insight into their working mechanisms. It is demonstrated that the overall effect of temperature on the device efficiency originates from the temperature dependence of the open-circuit voltage and the short-circuit current, while the fill factor remains approximately constant. Extensive modeling provides signs of band-like transport in the inhomogeneously coupled NC active layer and shows that the charge transport is dominated by diffusion. Moreover, via low temperature absorption and photoluminescence (PL) measurements, it is shown that the optical properties of PbS thin films before and after benzenedithiol (BDT) treatment exhibit very distinct behavior. After BDT treatment, both the optical density (OD) and PL are shifted to lower energies, indicating the occurrence of electronic wave function overlap between adjacent NCs. Decrease of the temperature leads to additional red-shift of the OD and PL spectra, which is explained by the well-known temperature dependence of the PbS NCs' bandgap. Moreover, BDT treated PbS NCs show unusual properties, such as decrease of the PL signal and broadening of the spectra at low temperatures. These features can be attributed to the partial relaxation of the quantum confinement and the opening of new radiative and nonradiative pathways for recombination at lower temperatures due to the presence of trap states.