The redox thermodynamics of cytochrome C at a 4,6-dimethyl-2-mercaptopyrimidine (DMMP), a new electron transfer promoter of cytochrome C, modified microband gold electrode (DMMP/Au) was investigated by cyclic voltammetry. The thermodynamic parameters of the electron-transfer reaction of cytochrome C at DMMP/Au electrode were estimated, The normal potential E(0'), the changes of entropy, enthalpy and Gibbs free energy, Delta S-0 , Delta H-0 and Delta G(0), for cytochrome C at 25 degrees C and pH 7.0 were 0.272 V (vs, NHE), -123.7 J . mol(-1). K-1, -63.1 kJ . mol(-1) and -26.2 kJ . mol(-1), respectively, The effects of temperature and pH on the thermodynamic parameters of cytochrome C were discussed, The E(0') vs, T plot shows remarkable biphasic character in an alkaline solution with a turning point at ca. 45 degrees C, whereas in an acid or neutral solution the E(0') values changed monotonically with temperature.