To develop a cement emulsified asphalt composite (CEAC) that can be sprayed under a plateau negative temperature environment, the effects of the water–solid ratio, calcium aluminate cement substitution rate, emulsified asphalt content, sand–binder ratio, and polyvinyl alcohol (PVA) fiber content on the spraying performance and rheological parameters of CEAC were explored through the controlled variable method. Additionally, the correlation between the spraying performance and rheological parameters of CEAC was established, and the optimal proportion of CEAC was determined. Then, the difference in frost resistance and pore structure between the cement slurry (CS) without emulsified asphalt and CEAC at the optimum proportion was analyzed. The results showed that the optimum proportions for sprayed CEAC were 0.14 water–solid ratio, 0.5 sand–binder ratio, 25% substitution of calcium aluminate cement, 5% emulsified asphalt content, and 1.5% PVA fiber volume mixing. The yield stress and plastic viscosity of CEAC were positively correlated with the build-up thickness, whereas the rebound rate and the latter showed a negative correlation. The spraying performance may be described by the rheological parameters; the ranges of yield stress and plastic viscosity of 2.37–3.95 Pa·s and 77.42–108.58 Pa, respectively, produced the best spray ability. After undergoing an equivalent number of freeze–thaw cycles, CEAC exhibited lower mass and strength loss rates compared to CS, thereby demonstrating superior frost resistance. In addition, the pore structure analysis showed that the difference in capillary and macropore contents was the main reason for the variability in frost resistance between CS and CEAC.