Based on 2N2222 NPN bipolar junction transistors (BJTs), synergistic effect between ionization and displacement defects induced by 3 MeV, 5 MeV and 10 MeV protons were researched. High-energy protons can be incident upon the silicon (Si) BJTs, producing displacement defects in silicon bulk and ionization damage in the oxide layer of BJTs, respectively. Both ionization and displacement damage result in the degradation of current gain of BJTs. At a given displacement dose, 10 MeV protons induce the maximum degradation of current gain of 2N2222 NPN BJTs, while 3 MeV protons cause the minimum degradation. In this case, non-ionizing energy loss (NIEL) methodology is not suitable to normalize the displacement damage induced by 3 MeV, 5 MeV and 10 MeV protons, which is attributed to the synergistic effect of ionization and displacement damage. The displacement defect centers in based-collector junction of 2N2222 transistor induced by 3 MeV, 5 MeV and 10 MeV proton exposures, were discovered and characterized by deep level transient spectroscopy (DLTS). Based on the comparison between the electrical parameters and the DLTS results, it is shown that, interface traps due to ionization damage induced by high-energy protons spread the emitter-base depletion layer, leading to the enhancement effects to displacement damage in the base-collector junction of NPN BJT. Meanwhile, bias voltage used during DLTS measurement influence characteristics of DLTS signals. With the increasing reverse bias, the value of $\Delta {\rm C}/{\rm C}$ for VO, ${{\rm V}_2}(= / -)$ , E4 and ${\rm V}_{2}(- /0) + {\rm E}5$ centers increases.