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The rotational spectra of two isotopologues (CF3(35)Cl-CO and CF3(37)Cl-CO) of the CF3Cl-CO adduct have been investigated and analyzed using supersonic-jet Fourier transform microwave spectroscopy, and found to have the features of a symmetric top. Rotational, centrifugal distortion, and nuclear quadrupole ((35)Cl and (37)Cl) coupling constants have been precisely obtained from high-resolution measurements. The two subunits of the complex are held together via a ClC halogen bond interaction. Information on the internal dynamics and the dissociation energy of the complex is provided. ; Italian MIUR/PRIN/2004033958_003 ; Italian MIUR/PRIN/2008KJX4SN_001 ; Italian MIUR/PRIN/2010ERFKXL_001 ; University of Bologna (RFO) ; Marie Curie fellowship/PIOF-GA-2012-32840 ; China Scholarship Council (CSC) ; Land Niedersachsen ; DFG