Liquid ammonia is an ideal zero-carbon fuel for internal combustion engines. High-pressure injection is a key technology in organizing ammonia combustion. Characteristics of high-pressure liquid ammonia injection is lack of research. Spray behaviors are likely to change when a high-pressure diesel injector uses liquid ammonia as its fuel. This study uses high-speed imaging with a DBI method to investigate the liquid penetration, width, and spray tip velocity of high-pressure liquid ammonia injection up to 100 MPa. Non-flash and flash boiling conditions were included in the experimental conditions. Simulation was also used to evaluate the results. In non-flash boiling conditions, the Hiroyasu model provided better accuracy than the Siebers model. In flash boiling conditions, a phenomenon was found that liquid penetration and spray tip velocity were strongly suppressed in the initial stage of the injection process, this being the “spray resistance phenomenon”. The “spray resistance phenomenon” was observed when ambient pressure was below 0.7 MPa during 0–0.05 ms ASOI and was highly related to the superheated degree. The shape of near-nozzle sprays abruptly changed at 0.05 ms ASOI, indicating that strong cavitation inside the nozzle caused by needle lift effects is the key reason for the “spray resistance phenomenon”.