Associated to each simplicial complex is a binary hierarchical model. We classify the simplicial complexes that yield unimodular binary hierarchical models. Our main theorem provides both a construction of all unimodular binary hierarchical models, together with a characterization in terms of excluded minors, where our definition of a minor allows the taking of links and induced complexes. A key tool in the proof is the lemma that the class of unimodular binary hierarchical models is closed under the Alexander duality operation on simplicial complexes.