The free jet millimeter-wave absorption spectrum of 1,3-cyclohexanedione has been investigated in the 59.6-74.4 GHz frequency range, and the rotational spectra of two conformational species, the chair-diketo and boat-diketo, and probably one excited vibrational state belonging to the chair-diketo form have been assigned. Quantum chemical calculations, performed at the B3LYP/6-311++G** and MP2/6-311++G** levels, were used to characterize the potential energy surface minima. The potential energy surface related to the interconversion of the observed diketonic species was modeled at the DFT level.