The third‐order optical nonlinearity χ(3) of porous silicon has been measured using the Z‐scan technique. Intensity dependent absorption was observed and attributed to a resonant two photon absorption process. The real and imaginary parts of χ(3) have been measured at 665 nm and found to be 7.5×10−9 esu and −1.9×10−9 esu, respectively. This constitutes a significant enhancement over crystalline silicon. All optical switching based on nonlinear absorption is demonstrated.