In this paper, a hybrid optimal control problem (HOCP) for the optimal heating of the three-way catalytic converter is solved. We propose a model for a hybrid vehicle that beneath State of Charge and fuel consumption includes thermal system states like engine cooling water temperature and catalytic converter temperature. Since models for noxious emissions with appropriate computational demand are not yet available for optimization purposes, an artificial state that resembles the emissions produced is introduced. A hybrid optimal control problem is then formulated for the beginning of the FTP-75 drive cycle whose target is to minimize the energy loss during the catalytic converter and engine cooling water heating phase. The corresponding input values to be optimized are continuous variables as ignition angle and cylinder charge as well as discrete decisions such as different injection schemes. As additional constraint, an upper limit is imposed on the artificial emissions state. A self-developed algorithm is then used to optimize the system with respect to the constraints and results are presented accordingly. The results obtained provide a valuable help for the calibration of the catalytic heating process and to obtain a solution that fulfills today's complex legal requirements.