Reactions of the phosphanyl-gold(I) precursor [(AuCl)(2) (bdppmapy)] ( 1; bdppmapy = N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine) with Na2S in a 1:1 or 1:2 molar ratio gave rise to one tetradecanuclear and one octanuclear Au(I) sulfido cluster, [Au,S-6(bdppmapy)5]Cl-2 (2) and [Au18S8(bdppmapy)6]Cl-2 (3), respectively. The former displays a new structural framework in gold cluster chemistry. Compounds 2 and 3 showed strong green luminescence and were employed as excellent imaging probes to selectively light up the lysosomes of living cells. Their long-term tracking of lysosomes can be achieved for up to 36 h, while tracking with commercial Lyso-Tracker Red under the same conditions was limited to 3 h. Our work demonstrated the possibility of constructing novel gold(I) sulfido clusters supported by special P-N hybrid ligands and the potential application of these clusters as long-term selective trackers of lysosomes in bioimaging.