The spray characteristics of liquid ammonia under various ambient pressures and temperatures were analyzed in a constant volume chamber to cover a wide range of superheat degrees. The injection pressure was set as 70 and 80 MPa with ambient pressure ranging from 0.2 to 4 MPa. The ambient temperature was 500 K. The results showed that the higher the injection pressure, the greater the kinetic energy obtained. The droplet fragmentation was enhanced, and the phenomenon of gradual separation of the gas–liquid region occurred with increasing injection pressure. Under flash boiling spray conditions, the spray developed faster than non-flash boiling and transition flash boiling spray under the same injection pressure. In addition, the flash boiling spray tip penetration of the gas and liquid increased more than that of cold spray, and the fluctuation of the late stage of the injection was relatively large. Therefore, the injection pressure has a greater effect on the spray tip penetration of flash boiling spray. Moreover, ambient pressure greatly influences the flare flash boiling spray. The spray resistance phenomenon was found during the spray development in the flare flash boiling condition. With the increase in ambient pressure, the spray tip penetration of flash boiling spray decreases due to the reduction in the pressure difference inside and outside the spray hole and the restriction of ambient gas. Meanwhile, owing to the low ambient pressure and ambient density, the liquid penetration in the initial phase of the flare flash boiling spray will be abnormally shorter than that of the non-flash boiling spray.