The molecular electrostatic potential surface of unsaturated, locally electron deficient molecules shows a positive region perpendicular to (a part of) the molecular framework. In recent years it has been shown both theoretically and experimentally that molecules are able to form noncovalent interactions with Lewis bases through this pi-hole. When studying unsaturated perfluorohalogenated molecules containing a higher halogen atom, a second electropositive region is also observed near the halogen atom. This region, often denoted as a sigma-hole, allows the molecules to interact with Lewis bases and form a halogen bond. To experimentally characterize the competition between both these noncovalent interactions, Fourier transform infrared and Raman spectra of liquefied noble gas solutions containing perfluorohalogenated ethylene derivatives (C2F3X; X= F, Cl, Br or I) and trimethylamine(-d(9)) were investigated. Analysis of the spectra shows that in mixed solutions of trimethylamine(-d(9)) and C2F4 or C2F3Cl lone pair(...)pi complex is present, while evidence for halogen bonded complex is found in solutions containing TMA(-d(9)) and C2F3Cl, C2F3Br or C2F3I. Analysis of the spectra shows that in mixed solutions of trimethylamine(-d9) and C2F4 or C2F3Cl lone pair(...)pi complex is present, while evidence for halogen bonded complex is found in solutions containing TMA(-d(9)) and C2F3Cl, C2F3Br or C2F3I. For all species observed, complexation enthalpies were determined, the values varying between -4. 9(1) and -24. 4 kJ mol(-1).