Excitation and emission spectra of Pb(2+) ions in Ca(10-x)Pb(x)(PO(4))(6)Cl(2) (0≤x≤10) compounds are investigated for various activator concentrations at different temperatures. A calcium-lead chlorapatite system shows a common apatitic structure and occurs as a continuous solid solution. An attempt to identify the pure electronic transitions between the ground and the excited levels of Pb(2+) is made. As a consequence of the two different sites in the apatite, two emission bands due to the [Formula: see text] (at room temperature) and [Formula: see text] (at low temperature) transitions of the Pb(2+) ions are observed. Decay times of Pb(2+) emission have been measured. Experimental data point out thermalization between (3)P(1) and (3)P(0) levels, for example, at very low temperature, the forbidden transition [Formula: see text] is the most intense. The overlap between the emission band of one site and the excitation band of the other site corresponds to an energy transfer phenomenon. Correlations between the luminescence results and the structural data are discussed.