Hybrid systems are dynamical systems characterized by the simultaneous presence of discrete and continuous variables. Model‐based control of such systems is computationally demanding. To this effect, explicit controllers which provide control inputs as a set of functions of the state variables have been derived, using multiparametric programming mainly for the linear systems. Hybrid polynomial systems are considered resulting in a Mixed Integer Polynomial Programming problem. Treating the initial state of the system as a set of bounded parameters, the problem is reformulated as a multiparametric Mixed Integer Polynomial optimization (mp‐MIPOPT) problem. A novel algorithm for mp‐MIPOPT problems is proposed and the exact explicit control law for polynomial hybrid systems is computed. The key idea is the computation of the analytical solution of the optimality conditions while the binary variables are treated as relaxed parameters. Finally, using symbolic calculations exact nonconvex critical regions are computed. © 2016 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 62: 3441–3460, 2016