Rhodium porphyrin catalyzed hydrogenation of the aliphatic carbon–carbon σ-bond of [2.2]paracyclophane with water has been examined with a variety of tetraarylporphyrins and axial ligands. Mechanistic investigations show that Rh^III(ttp)H, which can be derived from the reaction of [Rh^II(ttp)]₂ with water without a sacrificial reductant, plays an important role in promoting bimetallic reductive elimination to give the hydrogenation product.