The performance of a variety of high-level composite procedures, as well as lower-cost density functional theory (DFT)- and second-order perturbation theory (MP2)-based methods, for the prediction of absolute and relative R-X bond dissociation energies (BDEs) was examined for R = Me, Et, i-Pr and t-Bu, and X = H, CH3, OCH3, OH and F. The methods considered include the high-level G3(MP2)-RAD and G3-RAD procedures, a variety of pure and hybrid DFT methods (B-LYP, B3-LYP, B3-P86, KMLYP, 1311395, MPW1PW91, MPW1B95, BB1K, MPW1K, MPWB1K and BMK), standard restricted (open-shell) MP2 (RMP2), and two recently introduced variants of MP2, namely spin-component-scaled MP2 (SCS-MP2) and scaled-opposite-spin MP2 (SOS-MP2). The high-level composite procedures show very good agreement with experiment and are used to evaluate the performance of the lower-level DFT- and MP2-based procedures. The best DFT methods (KMLYP and particularly BMK) provide very reasonable predictions for the absolute heats of formation and R-X BDEs for the systems studied. However, all of the DFT methods overestimate the stabilizing effect on BDEs in going from R = Me to R = t-Bu, leading in some cases to incorrect qualitative behavior. In contrast, the MP2-based methods generally show larger errors (than the best DFT methods) in the absolute heats of formation and BDEs, but better behavior for the relative BDEs, although they do tend to underestimate the stabilizing effect on BDEs in going from R = Me to R = t-Bu. The potentially less computationally expensive SOS-MP2 method offers particular promise as a reliable method that might be applicable to larger systems.