The high resolution rotational spectrum of 2-(trifluoromethyl)pyridine in 2-20 GHz was recorded and analyzed.Spectroscopic parameters including rotational constants,nuclear quadrupole coupling constants of 14N as well as the centrifugal distortion constants were determined.The rotational spectra of five mono-substituted 13C and one 15N isotopologues were also measured and assigned in natural abundance.Experimental results complemented by ab initio calculations lead to an accurate determination of the skeleton structure.The values of the planar moment inertia Pcc were determined to be 44.46 u(A)2 for all the measured isotopologues,indicating a Cs symmetry of this molecule.The molecular electrostatic surface potential was calculated to illustrate the trifluoromethyl substitution effects on the electron distribution.