Photoluminescence (PL)-based sensing techniques have been significantly developed in practice due to their key advantages in terms of sensitivity and versatility of the approach. Recently, various nanostructured and hybrid materials have been used to improve the PL quantum yield and the spectral resolution. The near-infrared (NIR) fluorescence excitation has attracted much attention because it offers deep tissue penetration and it avoids the autofluorescence of the biological samples. In our study, we have shown both spectral and temporal PL modifications under two-photon excitation of quantum dots (QDs) placed in one-dimensional porous silicon photonic crystal (PhC) microcavities. We have demonstrated an up-to-4.3-fold Purcell enhancement of the radiative relaxation rate under two-photon excitation. The data show that the use of porous silicon PhC microcavities operating in the weak coupling regime permits the enhancement of the PL quantum yield of QDs under two-photon excitation, thus extending the limits of their biosensing applications in the NIR region of the optical spectrum.