In this review article, we give a new insight into the luminescence mechanism of porous silicon. First, we observed a “pinning” characteristic of photoluminescent peaks for as-etched porous silicon samples. It was explained as resulting from the discontinuous variation of the size of Si nanostructures, i.e. the size quantization. A tight-binding calculation of the energy band gap widening versus the dimension of nanoscale Si based on the closed-shell Si cluster model agrees well with the experimental observations. Second, the blue-light emission from porous silicon was achieved by using boiling water treatment. By investigating the luminescence micrographic images and the decaying behaviors of PL spectra, it has been shown that the blue-light emission is believed to be originated from the porous silicon skeleton rather than the surface contaminations. The conditions for achieving blue light need proper size of Si nanostructures, low-surface recombination velocity, and mechanically strong skeleton. The fulfillment of these conditions simultaneously is possible but rather critical. Third, the exciton dynamics in light-emitting porous silicon is studied by using the temperature-dependent and picosecond time-resolved luminescence spectroscopy. A direct evidence of the existence of confined excitons induced by the quantum size effect has been revealed. Two excitation states are found to be responsible for the visible light emission, i.e. a higher lying energy state corresponding to the confined excitons in Si nanostructures and a lower lying state related with surfaces of Si wires or dots. A picture of the carrier transfer between the quantum confined state and the surface localized state has been proposed. Finally, we investigated the transient electroluminescence behaviors of Au/porous silicon/Si/Al structure and found it is very similar to that of an ordinary p-n junction light-emitting diode. The mechanism of electroluminescence is explained as the carrier injection through the Au/porous silicon Schotky barrier and the porous silicon/p-Si heterojunction into the corrugated Si wires, where the radiative recombination of carriers occurs.