The 4‐(thiolmethyl)‐7‐(diethylamino)‐2H‐chromen‐2‐one ligand has been synthesized and used as chromophore in several mono‐ and dinuclear gold(I) compounds that contain a phosphane at the second coordination position. Four final products were able to obtain in pure form containing one coumarin and one phosphane ligand in the case of PTA (1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.13.7]decane) and PPh3 (triphenylphosphine); one coumarin and two gold(I)‐phosphane groups in the case of phosphane=DAPTA (3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane) and two coumarin and two gold(I) atoms in the case of phosphane=DPEphos (bis[(2‐diphenylphosphino)phenyl]ether), when it was used a diphosphane. Other diphosphane ligands used were not able to give the desired products in pure form. The luminescent properties of the compounds are governed by the fluorescence of the coumarin moiety in all compounds both for measurements carried out in solution and also immobilized in PMMA organic matrix. Phosphorescence emission can be detected in all cases at 77 K both for the uncoordinated coumarin ligand and the gold(I) derivatives, being more favoured in the presence of the gold(I) heavy atom. The compounds have been used as photosensitizers to generate 1O2 with moderate quantum yields values.