A solution to the optimal problem for determining vector fields which maximize (resp. minimize) the transition probabilities from one location to another for a class of reflecting diffusion processes is obtained in the present paper. The approach is based on a representation for the transition probability density functions. The optimal transition probabilities under the constraint that the drift vector field is bounded by a constant are studied in terms of the HJB equation. In dimension one, the optimal reflecting diffusion processes and the bang-bang diffusion processes are considered. We demonstrate by simulations that, even in this special case, the optimal diffusion processes exhibit an interesting feature of phase transitions. We also solve an optimal stochastic control problem for a class of stochastic control problems involving diffusion processes with reflection.