This paper considers the class of deterministic continuous-time optimal control problems (OCPs) with piecewise-affine (PWA) vector field, polynomial Lagrangian and semialgebraic input and state constraints. The OCP is first relaxed as an infinite-dimensional linear program (LP) over a space of occupation measures. This LP is then approached by an asymptotically converging hierarchy of linear matrix inequality (LMI) relaxations. The relaxed dual of the original LP returns a polynomial approximation of the value function that solves the Hamilton-Jacobi-Bellman (HJB) equation of the OCP. Based on this polynomial approximation, a suboptimal policy is developed to construct a state feedback in a sample-and-hold manner. The results show that the suboptimal policy succeeds in providing a suboptimal state feedback law that drives the system relatively close to the optimal trajectories and respects the given constraints.