Cementitious capillary crystalline waterproofing (CCCW) effectively improves the durability of concrete structures by generating penetration crystallization through active substances. In order to deeply study the preparation and application performance of active materials of CCCW, hydroxyethylidene diphosphonic acid (HEDP) complexing agent, sodium silicate precipitant, calcium hydroxide and nano-silica (NS) were selected to form the active masterbatch, and the four-factor, four-level orthogonal experimental design was used to determine the main factors affecting the compressive strength of concrete, the quality of water resistance and the resistance to sulphate erosion through the significance analysis, and the optimal group distribution ratio was determined by the comprehensive efficacy coefficient combined with the coefficient of resistance to sulphate erosion. The main influencing factors on the compressive strength, water resistance and sulfate erosion resistance of concrete were determined by significance test, and the optimal group ratio of active masterbatch was investigated by the comprehensive efficacy coefficient combined with the sulfate erosion resistance coefficient, and the microscopic mechanism was analyzed by scanning electron microscope and X-ray diffraction(XRD) at the same time. The results show that sodium silicate affects the hydration process of cement and the excess will make the internal structure loose, and has the most significant effect on the compressive strength of concrete. The optimal dosages of HEDP, sodium silicate, calcium hydroxide and NS are 0.15%, 1%, 1% and 3% of the mass of cement, respectively. The active masterbatch can effectively change the morphology of caliche, so that the structural compactness is increased. The study can provide important technical references for the improvement and application of CCCW.