This work reports the photophysical properties of copper (I) complexes and CdTe QDs loaded in a mesoporous silica matrix obtained by sol-gel method with an average pore diameter of 10 nm. The colloidal suspension of CdTe, synthesized in aqueous phase, presents maximum emission at λem = 520 nm with full width at half maximum (FWHM) of 45 nm. While loaded into the solid SiO2 matrix, the QD emission had small shift, according to the type of incorporation strategy. The complexes Cu4I4py4 (1) and C30H28N2O2PCuI (2) incorporated on mesoporous silica showed a shift in emission of λem = 580 nm to 645 nm and λem = 660 nm to 575 nm, respectively. This shift of the emission is caused by distortion of the molecular complex, in the MLCT excited state, inside the matrix, known as rigidochromic effect. Also, a sensitivity of these hybrids materials (1@SiO2 and 2@SiO2) was observed to oxygen. The mesoporous matrix dispersed the molecules of the complex, so as to enable a reversible interaction with oxygen in the center of the metal that quenches of luminescence and provides a new functionality to the complex. The new functional materials proposed in this study have potential for applications in optical materials devices.