A system includes a catalyst light-off module that selectively generates a first signal based on an engine coolant temperature and an estimated exhaust enthalpy, a setpoint module that selectively initiates a catalyst light-off period in response to receiving the first signal and that generates a desired exhaust enthalpy, and a first model predictive control (MPC) module that generates predicted parameters based on a model of an engine and a set of possible target values, generates a cost for the set of possible target values based on the predicted parameters and the desired exhaust enthalpy, and selects the set of possible target values from multiple sets of possible target values based on the cost. The system also includes an engine actuator module that adjusts an actuator of the engine based on at least one of the target values.