The knowledge of capture properties of electrically active defects is of primary importance as it helps to understand which deep states are effective in controlling the excess free carriers’ lifetime. Combining DLTS capture experiments with thermal emission measurements enables an overall thermodynamic description of deep states, thus making it possible to characterize recombination centers in semiconductor-based devices. In the present study, junction DLTS capture rate measurements were employed to extract the true capture cross-sections (inversely proportional to the carrier lifetime) and capture energy barriers for the main lifetime limiting defects in 4H-SiC(silicon carbide). A peculiar forward bias dependence of the capture parameters was observed for the shallow boron (B) hole trap. Capture rate measurements on the deep boron (D-center) trap also evidenced the presence of two capture mechanisms, thus allowing discrimination of D<inf>1</inf> and D<inf>2</inf> deep states within the D-center DLTS peak. The results were combined with activation energies and apparent capture cross-sections to obtain the free energy (ΔG) of electronic activation for the analysed deep states.