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This long-term fertilization experiment was conducted since 1981, included non-fertilization (NF), chemical fertilizer (CF), double chemical fertilizer (DCF) and chemicals with organic fertilizer (COF). In 2017, soil samples were collected at the tillering, heading and maturity stages of early-season rice (Oryza sativa L.). The activities of urease (UR), α-glucosidase (AG), glucosaminidase (NAG), β-1,4 glucosidase (BG), β-cellobiosidase (CBH), β-xylosidase (BXYL), acid phosphatase (ACP), phenoloxidase (POX) and peroxidase (PER) were measured. The activities of AG, NAG, BG, CBH, BXYL, ACP and POX in the maturity stage were significantly higher than in the tillering stage by 343.0%, 153.4%, 55.0%, 8.5%, 1791.5%, 1237.7% and 1179.4%, respectively. Compared with the CF treatment, the activities of UR, AG, BG, and POX in the COF treatment increased by 33.5%, 23.3%, 19.5% and 40.1%, respectively. Meanwhile, both CBH and ACP in the COF treatment were higher than in the DCF treatment by 33.4% and 66.7%, respectively. A significant relationship was identified between UR/PER activities and soil available nitrogen, phosphorus, potassium/rice biomass using the redundancy analysis method. Therefore, the application of organic and chemical fertilizers could increase most enzymatic activities and soil productivity. UR and PER were key factors indicating soil nutrient turnover and rice growth. [ABSTRACT FROM AUTHOR]