A sequence $σ$ of $p$ non-negative integers is unigraphic if it is the degree sequence of exactly one graph, up to isomorphism. A polyhedral graph is a $3$-connected, planar graph. We investigate which sequences are unigraphic with respect to the class of polyhedral graphs, meaning that they admit exactly one realisation as a polyhedron. We focus on the case of sequences with largest entry $p-2$. We give a classification of polyhedral unigraphic sequences starting with $p-2,p-2$, as well as those starting with $p-2$ and containing exactly one $3$. Moreover, we characterise the unigraphic sequences where a few vertices are of high degree. We conclude with a few other examples of families of unigraphic polyhedra.