The microcanonical temperature of an isolated molecule is derived in terms of Boltzmann and Gibbs volume entropies within the quantum harmonic vibrational and equivalent degenerated model approximations. The effects of the entropy functional choice and various approximations are examined. The difference between Boltzmann and Gibbs volume temperatures is negligible for molecules bigger than ten atoms. However, it is significant for smaller systems, opening a way to probe them experimentally. A simple, analytical expression of the temperature as a function of the vibrational energy is provided, allowing predictions with a ±3% margin of error compared to the exact harmonic estimate. The microcanonical temperature is discussed and exemplified with polycyclic aromatic hydrocarbon molecules and other molecules of astrophysical interest.