The intramultiplet relaxation of Cd(53P2) was studied by using pump-and-probe techniques. The following thermally averaged cross sections were obtained for the 3P2→3P1 and 3P2→3P0 transitions induced by collisions with N2 and CO at 63 σ20(N2) = 1.2, σ21(CO) = 20.9 and σ20(CO) = 7.6 in units of 10-16 cm2. Comparison of these cross sections with those fo overall deactivation shows that the intramultiplet relaxation processes are the major exit channels and that the deactivation to the ground state is minor. The curve crossing probabilities were calculated for the Cd(53P2)+N2 collisions by employing a semiclassical model. It was revealed that Cd+-N2- ionic complexes play an important role.