The heats of formation of CF3, its cation and anion, CF4, C2F4, and :CFCF3 have been calculated at high levels of ab initio molecular orbital theory. Geometries and frequencies were determined, in general, with second-order perturbation theory. Total energies based on coupled cluster calculations with perturbative triples were determined with basis sets up through augmented quadruple-zeta in quality and were subsequently extrapolated to the complete one-particle basis set limit, so as to further reduce the basis set truncation error. Due to its importance as a standard, CF4 was studied with even larger basis sets. Additional improvements in the atomization energy were achieved by applying corrections due to core/valence correlation, scalar relativistic, and atomic spin-orbit effects. Zero-point energies were based on the experimental fundamentals, when available, and harmonic frequencies obtained from MP2/cc-pVTZ calculations. Missing frequencies for :CFCF3 were calculated at the MP2/DZP level. The calculated heats of formation (kcal/mol) are as follows: Delta H-f(CF4) = -221.8 +/- 1.1 vs -221.6 +/- 0.3 (expt); Delta H-f(CF3) = -111.9 +/-1.0 vs -111.7 +/- 1.0 (expt); Delta H-f(CF3+) = 98.0 +/- 1.2 vs 99.8 +/- 2.8 (expt); Delta H-f(CF3-) = -151.9 +/- 0.7 vs -154.9 +/- 1.0 (expt); Delta H-f(C2F4) = -159.8 +/- 1.5 vs -156.6 +/-0.7 (expt); and Delta H-f(:CFCF3) = -122.6 +/- 1.5, all at 0 K. These values are used to calculate a variety of bond energies and molecular energetics.