To improve the performance of shotcrete in high-altitude and low-temperature environments, emulsified asphalt shotcrete (EASC), which can be used in negative-temperature environments, was prepared by using low-freezing-point emulsified asphalt, calcium aluminate cement, and sodium pyrophosphate as modified materials. The effect of emulsified asphalt on the performance of shotcrete was investigated through concrete spraying and indoor tests. Then, the modification mechanism of emulsified asphalt with respect to EASC was analyzed by combining scanning electron microscopy images and the pore structure characteristics of EASC. The results showed that in a negative-temperature environment, the incorporation of emulsified asphalt delayed the formation of the peak of the cement hydration exotherm, slowed the rate of the cement hydration exotherm, reduced the thermal perturbation of permafrost by EASC, increased the cohesion of the concrete, improved the bond strength between EASC and permafrost, and reduced the rate of rebound. The mechanical strength of the studied EASC decreased upon increasing the amount of emulsified asphalt in the admixture, and its resistance to cracking gradually improved. A content of less than 5% emulsified asphalt could improve the internal pore structure of EASC, thus improving its durability. Increasing the content of emulsified asphalt affected the hydration process of the cement, and the volume content of the capillary pores and macropores increased, which reduced the durability of the EASC.