We present the performances of Li-based compounds used as scintillating bolometer for rare decay studies such as double-beta decay and direct dark matter investigations. The compounds are tested in a dilution refrigerator installed in the underground laboratory of Laboratori Nazionali del Gran Sasso (Italy). Low temperature scintillating properties are investigated by means of different radioactive sources, and the radio-purity level for internal contaminations are estimated for possible employment for next generation experiments.