UV frequency metrology has been performed on the a 3 Π -X 1 Σ + (0,0) band of various isotopologues of CO using a frequency-quadrupled injection-seeded narrow-band pulsed Titanium:Sapphire laser referenced to a frequency comb laser. The band origin is determined with an accuracy of 5 MHz (δν/ν = 3 · 10 −9 ), while the energy differences between rotational levels in the a 3 Π state are determined with an accuracy of 500 kHz. From these measurements, in combination with previously published radiofrequency and microwave data, a new set of molecular constants is obtained that describes the level structure of the a 3 Π state of 12 C 16 O and 13 C 16 O with improved accuracy. Transitions in the different isotopologues are well reproduced by scaling the molecular constants of 12 C 16 O via the common mass-scaling rules. Only the value of the band origin could not be scaled, indicative of a breakdown of the Born-Oppenheimer approximation. Our analysis confirms the extreme sensitivity of two-photon microwave transitions between nearly-degenerate rotational levels of different Ω-manifolds for probing a possible variation of the proton-to-electron mass ratio, µ = mp/me, on a laboratory time scale.