The interaction of haemopexin and albumin with TPPS4 was studied by measuring the absorption and fluorescence spectra. Haemopexin was found to have one strong TPPS4 binding center (Ka = 3 x 10(7) M-1). 2. Haem-haemopexin complex appears to have no specific binding site for TPPS4. Occupation of the specific binding center of haemopexin molecule by a haem abolishes TPPS4 binding. 3. Albumin was found to possess one strong TPPS4 binding center (Ka = 3 x 10(6) M-1) besides two or three weak binding sites (Ka = 2 x 10(5) M-1). 4. Haem-albumin complex possesses only one weak TPPS4 binding site (Ka = 7 x 10(5) M-1). These observations suggest identity of primary binding sites of TPPS4 and haem on albumin molecule.