We study the barrier that gives the optimal time to exercise an American option written on a time-dependent Ornstein–Uhlenbeck process, a diffusion often adopted by practitioners to model commodity prices and interest rates. By framing the optimal exercise of the American option as a problem of optimal stopping and relying on probabilistic arguments, we provide a non-linear Volterra-type integral equation characterizing the exercise boundary, develop a novel comparison argument to derive upper and lower bounds for such a boundary, and prove its Lipschitz continuity in any closed interval that excludes the expiration date and, thus, its differentiability almost everywhere. We implement a Picard iteration algorithm to solve the Volterra integral equation and show illustrative examples that shed light on the boundary’s dependence on the process’s drift and volatility.