The quantum yield (phi zz) for the E--> photoisomerization of bilirubin (BR) bound to human serum albumin (HSA) under laser light irradiation has been evaluated with absorbance spectroscopy implemented by the high-performance liquid chromatography technique. The value at 458 nm is about 0.2, four times smaller than the value previously reported in the literature. As for the Z-->E configurational and the structural photoisomerization processes, the quantum yield varies with excitation wavelength, from 0.23 in the blue to 0.16 in the green. The sum of the quantum yields of the Z<-->E configurational photoisomerization reactions is 0.2-0.3 in the blue-green spectral region, thus giving direct evidence of the existence of internal conversion processes of the BR-HSA complex which compete with configurational photoisomerization. An evaluation of the quantum yields of the Z<-->E reactions for filtered broad-band light excitation in the 390-530 nm spectral region from data already published in the literature is also reported. Good agreement with our data of the quantum yields phi ZZ and phi ZE is found, despite the diversity of the experimental procedures in the two cases.