In this paper, we study the new better than used in expectation (NBUE) and new worse than used in expectation (NWUE) properties of Markov renewal processes. We show that a Markov renewal process belongs to a more general class of stochastic processes encountered in reliability or maintenance applications. We present sufficient conditions such that the first-passage times of these processes are new better than used in expectation. The results are applied to the study of shock and repair models, random repair time processes, inventory, and queueing models.