We consider a second-order elliptic operator L in skew product of an ordinary differential operator L1 on an interval (a, b) and an elliptic operator on a domain D2 of a Riemannian manifold such that the associated heat kernel is intrinsically ultracontractive. We give criteria for criticality and subcriticality of L in terms of a positive solution having minimal growth at η (η = a, b) to an associated ordinary differential equation. In the subcritical case, we explicitly determine the Martin compactification and Martin kernel for L on the basis of [24]; in particular, the Martin boundary over η is either one point or a compactification of D2, which depends on whether an associated integral near η diverges or converges. From this structure theorem we show a monotonicity property that the Martin boundary over η does not become smaller as the potential term of L1 becomes larger near η.