Optical properties of YOCl:Eu3+ powders and EuCl3 solution embedded in nanoporous glass were investigated. In comparison with those in the normal micro-powder phosphor, emission spectra of Eu3+ in nano-YOCl:Eu3+ became much broader. Blueshift (7 nm) was observed in the lines due to 5D0→7F2 transition and Eu-O charge transfer excitation band. The ratio intensities of the 5D0→7F1 transition to the 5D0→7F2 transition of Eu3+ became larger and changed at different excitation wavelengths (254 nm and 393 nm). In comparison with those in the bulk EuCl3 solution, nano-EuCl3 solution had neither small size effects nor quantum confinement effects. Luminescence due to upper levels of Eu3+ in the nano-solution was enhanced. This approach also combines the advantages of nanoporous glass in offering good chemical shielding and mechanical support. The results obtained indicate that this approach likely may make a new kind of luminescent material.