The microwave spectrum of bromoperfluoroacetone has been observed and reported for the first time on a newly constructed CP-FTMW spectrometer located at Missouri S&T operational in the 6–18GHz region of the electromagnetic spectrum. Rotational constants, centrifugal distortion constants, and all components of the nuclear quadrupole coupling tensor were determined for both the 79 and 81 isotopologues of bromine and have been reported. The spectrum is densely populated with transitions and the need for the more accurate theory of W.C. Bailey was needed for adequate assignment of >2000 transitions. Included in the spectrum were dipole forbidden ΔJ=2 and x-type transitions. Second moments and Kraitchman position of the bromine have been presented to help identify the experimental structure. Quadrupole coupling tensor analyses were carried out to show that the electric field gradient in bromine changes dramatically upon fluorination when compared to its chlorine counterpart. Also, this change represents an increase in the electric field gradient, suggesting more covalent C-Br bonding. Dipole forbidden transitions have been observed and found to be always linked through a dipole allowed transition, but are not necessarily linked through one singular off-diagonal term. Notably, a select few of the dipole forbidden transitions are facilitated through a third mixing state not previously found in the literature.