Aiming at the issue of crystallization and blockage of drainage system due to the massive calcium loss from the tunnel shotcrete, a self-designed tunnel seepage crystallization modelling system was developed. This system was produced in conjunction with the initial tunnel support shotcrete construction and drainage pipe installation, and is capable of simulating both the seepage process of groundwater in the shotcrete and the process of crystallization in the drainage pipe. Based on three different mechanisms of anti-crystallization, which include absorbing free calcium, reducing the porosity and increasing hydrophobicity, antialkali agent, nano-calcium carbonate, and silane were selected to test, respectively. Firstly, the suitable dosing ranges of these three external admixtures for resisting calcium loss in shotcrete were determined by single factor tests, which were 7%–11%, 4%–8%, and 0.3%–0.5%, respectively. Thereafter, the response surface method was employed to evaluate the interaction of antialkali agent, nano-calcium carbonate and silane on calcium loss in shotcrete, and to establish the relationship between them, and thus to determine the admixture ratio that can effectively reduce calcium loss crystallization in shotcrete, with the optimal admixture amounts of antialkali agent being 9.242%, nano-calcium carbonate 4.889% and silane 0.366%. Lastly, the reliability of the model test results was verified by the microscopic analysis, and the results showed that the total amount of calcium dissolution in the optimized group could be reduced by 75% compared with the blank control group, and was basically consistent with that derived from the response surface regression model, validating the high accuracy of the buildup response surface regression model. The present study can provide some ideas and references for reducing the seepage crystallization behavior of groundwater in the initial tunnel support shotcrete.