Loop heat pipe (LHP) is an efficient phase-change heat transfer device which has been widely applied in cooling high-power electronics on ground and in spacecraft. In previous work, a novel LHP coupled with vapor-driven jet injector (VDJI) has been proved to be feasible and shows excellent performance, namely LHPI. However, due to the lack of pressure data during LHP operation, the coupling mechanisms of VDJI and LHP remain unknown. Especially, the heat-mass transfer between high-speed vapor and subcooled liquid inside VDJI, which has great influence on the LHPI, need to be investigated to guide the design of the LHPI. In this paper, the start-up process, steady-state operation characteristic of LHPI and internal flow field of VDJI were investigated experimentally and numerically. By using the pore-forming sintering and integrated sintering method, the bi-porous wick was prepared and embedded on the base plate surface of evaporator, which brought a significant improvement in its performance. The results indicated that the LHPI could operate under a power of 600 W (50.0 W/cm2) without dry-out. Maintaining the heating wall temperature within 85 °C, the minimum thermal resistance of the LHPI with bi-porous and integrated sintered wick was below 0.18, and the maximum heating power can reach up to 404 W, which are 60% lower and 52.5% higher than mono-porous wick, respectively. In addition, four operation modes of VDJI were classified as low-efficiency mode, normal-injection mode, restricted expansion mode and superheated mode. The operation modes of VDJI had great influence on the performance of LHPI. In normal-injection mode, the entrainment ratio of VDJI exceeded 100, which resulted in the lowest thermal resistance of LHPI. For long-term operation of LHPI, the VDJI is suggested keep operating in normal-injection mode. Moreover, by using 3D numerical simulation method, the internal flow structure of the VDJI was obtained to gives an insight into mechanisms of these four operation modes. The numerical results showed the profile of compression waves and confirmed the existence of condensation shock wave in VDJI.