The interaction of water-soluble C60 derived fullerols with bovine serum albumin (BSA) in physiological environment was studied in detail by the fluorescence method. Experiments showed that the interaction of fullerols with BAS is mainly in the manner of non-covalent hydrogen bond. Based on the measurements of fluorescence intensity, the apparent binding constant K and the binding site number n were obtained with K=4000 and n=1, and the energy transfer efficiency in the reaction is 0.63. Besides, the effects of metallic ions such as Cu2+, Fe3+ and Cr(VI) on the interaction of fullerols with BSA were investigated. It was found that the effects of the metallic ions are quite different from each other. Low concentrations of Cu2+ can promote the interactions between fullerols and BSA, while high concentrations of Fe3+ or Cr(VI) favorite the interactions between fullerols and BSA.