From the partially resolved rotational structure of six vibrational bands at high resolution, a vibrational progression in the 22 400-22 900 cm(-1) region has been assigned to a CaXe[(3)Sigma(-)]<-- Ca(4s4p pi P-3(0)). Xe[(3)Pi(0)(-)] transition. It is suggested that the CaXe[(3)Sigma(-)] state observed is a "mixed" state, having both Ca(4p pi 4p pi P-3(J)). Xe[(3)Sigma(-)] and Ca(3d pi 4p pi D-3(J)). Xe[(3)Sigma(-)] character due to an adiabatic avoided crossing between the two diabatic states.