The invention provides a water-soluble composite fertilizer with high phosphorus and calcium. The composite material comprises, by weight, 10-60 parts of a potash fertilizer, 10-60 parts of a phosphate fertilizer, 10-30 parts of a calcium fertilizer, 2-20 parts of urea and 0.1-5 parts of an anti-caking agent. The invention also provides a preparation method of the water-soluble composite fertilizer with high phosphorus and calcium. The composite fertilizer has the characteristics of high content of total nutrients, stable physical and chemical properties, good powder fluidity, no caking, precipitation or gas bloating at high temperature, low temperature or normal temperature, and good solubility. Phosphoric acid or phosphate is added to a solution obtained by dissolving the composite fertilizer in water to provide an acidic condition in order to make phosphate radicals and calcium ions simultaneously stably coexist in a liquid phase and avoid the generation of calcium phosphate and other insoluble precipitates. The water-soluble composite fertilizer effectively improves the fertilizer utilization rate, has highly concentrated nutrients, is suitable for large-area automatic fertilization, can obviously improve the fertilizing efficiency, and also has the advantages of time saving, labor saving, fertilizer saving and fast fertilizer efficiency.