The complex [Ru(5,6-Me2Phen)3]tfpb2 has been examined as a solid-state benzene and oxygen sensor. The crystalline solid undergoes a reversible vapochromic shift of the emission λmax to higher energy in the presence of benzene. Additionally, in the presence of oxygen the solid exhibits linear Stem-Volmer quenching behavior. When simultaneously exposed to benzene vapor and oxygen the crystals uptake benzene which inhibits the diffusion of oxygen in the lattice; very little quenching is observed. However, when benzene is removed from the carrier gas, partial loss of benzene occurs and oxygen diffusion is restored resulting in quenching of the emission. The practicality of this crystalline solid as a benzene sensor was investigated by examination of a lower concentration of benzene vapor (0.76%).