The microwave spectra of four isotopologues of the CHClF(2)-HCCH dimer have been measured and used to determine the structure of the complex. An initial scan over the 7-18 GHz region using the chirped-pulse microwave spectrometer at the University of Virginia provided initial assignments of the (35)Cl and (37)Cl isotopologues, with two additional H(13)C(13)CH species assigned using the resonant cavity Balle-Flygare microwave spectrometer at Eastern Illinois University. For the most abundant isotopologue, the rotational constants and quadrupole coupling constants are: A = 3301.21(4) MHz, B = 1353.4268(19) MHz, C = 1153.7351(18) MHz, χ(aa) = 34.681(12) MHz, χ(bb) = -69.70(3) MHz, χ(cc) = 35.02(2) MHz and χ(ab) = -8.8(3) MHz, in good agreement with ab initio calculations at the MP2/6-311++G(2d,2p) level. The alignment of CHClF(2) with respect to acetylene reveals a C-Hπ interaction, with a secondary C-ClH-C interaction also present between the two monomers. The fitted distance between the CHClF(2) hydrogen atom and the center of the triple bond is 2.730(6) Å, the distance between the chlorine atom and the acetylenic hydrogen is 3.061(38) Å, and the C-Hπ angle is 148.2(6)°. In addition, the centrifugal distortion constants give an estimate of the binding energy for the weak interaction of about 4.9(5) kJ mol(-1), in reasonable agreement with several similar complexes.