The potential energy surface (PES) of the general anesthetic fluoroxene (2,2,2-trifluoroethyl vinyl ether) was probed in a supersonic jet expansion using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and theoretical calculations. The PES is dominated by a single conformation, as other stable minima are shown to kinetically relax in the expansion to the global minimum. Consistently, the rotational spectrum reveals a single conformation. Fluoroxene adopts a CS heavy-atom planar skeleton structure in the gas phase, with a cis-trans conformation (cis for the CH2[double bond, length as m-dash]CH-O-CH2- and trans for the [double bond, length as m-dash]CH-O-CH2-CF3 part). The sensitivity of a recently-built CP-FTMW spectrometer at the UPV/EHU is demonstrated by the detection of five isotopologues of fluoroxene in natural abundance, corresponding to the (13)C and (18)O monosubstituted species. The rS and r0 structures were determined and are in good agreement with theoretical predictions using the MP2, B3LYP and M06-2X methods.