Angular dependence of rotational and vibrational temperatures of product CO2 were studied in CO oxidation on a Pd polycrystalline surface by means of chemiluminescence measurements. Rotational temperature (T-rot) and vibrational temperature (T-vib) showed minimum values at the surface normal and significantly increased as the desorption angle increased. T-rot and T-vib became higher when the ratio of exposure of O-2 to that of CO increased. These angular dependences are quite different from those on Pd(111).