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We report on the systematic characterization of the optical properties of diamond color centers based on Pb impurities. An ensemble photoluminescence analysis of their spectral emission was performed at different excitation wavelengths in the 405–520 nm range and at different temperatures in the 4–300 K range. The series of observed spectral features consist of different emission lines associated with Pb-related defects. Finally, a room-temperature investigation of single-photon emitters under 490.5 nm laser excitation is reported, revealing different spectral signatures with respect to those already reported under 514 nm excitation. This work represents a substantial progress with respect to previous studies on Pb-related color centers, both in the attribution of an articulated series of spectral features and in the understanding of the formation process of this type of defect, thus clarifying the potential of this system for high-impact applications in quantum technologies.