In order to reveal the mechanism of silicon (Si) fertilizer in improving nitrogen (N) and phosphorus (P) nutrient availability in paddy soil, we designed a series of soil culture experiments by combining application of varying Si fertilizer concentrations with fixed N and P fertilizer concentrations. Following the recommendations of fertilizer manufacturers and local farmers, we applied Si in concentrations of 0, 5.2, 10.4, 15.6, and 20.8 μg/kg. At each concentration of added Si, the availability of soil N and P nutrients, soil microbial activity, numbers of ammonia-oxidizing bacteria and P-decomposing bacteria which means that the organic P is decomposed into inorganic nutrients which can be absorbed and utilized by plants, and urease and phosphatase activity first increased, and then decreased, as Si was added to the soil. These indicators reached their highest levels with a Si application rate of 15.6 μg/kg, showing values respectively 19.78%, 105.09%, 8.34%, 73.12%, 130.36%, 28.12%, and 20.15% higher than those of the controls. Appropriate Si application (10.4 to 15.6 µg/kg) could significantly increase the richness of the soil microbial community involved in cycling of N and P nutrients in the soil. When the Si application rate was 15.6 μg/kg, parameters for characterizing microbial abundance such as sequence numbers, operational taxonomic unit (OTU) number, and correlation indices of microbial community richness such as Chao1 index, the adaptive coherence estimator (ACE) index, Shannon index, and Simpson index all reached maximum values, with amounts increased by 14.46%, 10.01%, 23.80%, 30.54%, 0.18%, and 2.64%, respectively, compared with the control group. There is also a good correlation between N and P mineralization and addition of Si fertilizer. The correlation coefficients between the ratio of available P/total P (AP/TP) and the number of ammonia-oxidizing bacteria, AP/TP and acid phosphatase activity (AcPA), AP/TP and the Shannon index, the ratio of available N/total amount of N (AN/TN) and the number of ammoniated bacteria, and AN/TN and AcPA were 0.9290, 0.9508, 0.9202, 0.9140, and 0.9366, respectively. In summary, these results revealed that enhancement of soil microbial community structure diversity and soil microbial activity by appropriate application of Si is the key ecological mechanism by which application of Si fertilizer improves N and P nutrient availability.