Severe early defoliation has become an important factor restricting the development of the pear industry in southern China. However, the assembly patterns of microbial communities and their functional activities in response to the application of bioorganic fertilizer (BIO) or humic acid (HA) in southern China’s pear orchards remain poorly understood, particularly the impact on the early defoliation of the trees. We conducted a 3-year field experiment (2017–2019) in an 18-year-old ‘Cuiguan’ pear orchard. Four fertilization schemes were tested: local custom fertilization as control (CK), CK plus HA (CK-HA), BIO, and BIO plus HA (BIO-HA). Results showed that BIO and BIO-HA application decreased the early defoliation rate by 50–60%, and increased pear yield by 40% compared with the CK and CK-HA treatments. The BIO and BIO-HA application significantly improved soil pH, available nutrient content, total enzyme activity and ecosystem multifunctionality, and also changed the structure of soil bacterial and fungal communities. The genus Acidothermus was positively correlated with the early defoliation rate, while the genus Rhodanobacter was negatively correlated. Additionally, random forest models revealed that the early defoliation rate could be best explained by soil pH, ammonium content, available phosphorus, and total enzyme activity. In conclusion, application of BIO or BIO mixed with HA could have assembled distinct microbial communities and increased total enzyme activity, leading to significant improvement of soil physicochemical traits. The increased availability of soil nutrient thus changed leaf nutrient concentrations and alleviated the early defoliation rate of pear trees in acid red soil in southern China.