Acidification can seriously affect the growth of tea trees and the yield and quality of tea leaves. In this study, we analyzed the effects of acidification on the physicochemical properties, microorganisms and metabolites of tea rhizosphere soils with different pH values, and the results showed that with the increase of soil pH, the organic matter content, cation exchange capacity, microbial biomass carbon, microbial biomass nitrogen, microbial respiration intensity, bacterial number and actinomyces number in tea rhizosphere soil all showed an increasing trend, while the fungi number decreased. The results of soil metabolite analysis showed that 2376, 2377 and 2359 metabolites were detected in tea rhizosphere soil with pH values of 3.29, 4.74 and 5.32, respectively, and the number of similar compounds reached 2331, accounting for more than 98%. The results of soil metabolite content analysis showed that with the increase of soil pH, the total contents of metabolite of tea rhizosphere soil increased significantly. The results of correlation analysis between physicochemical indexes of soil and microorganisms and soil metabolites showed that physicochemical indexes of soil and microorganisms were significantly correlated with 221 soil metabolites, among which 55 were significantly positively correlated and 166 were significantly negatively correlated. Based on correlation interaction network analysis, 59 characteristic compounds were obtained and divided into 22 categories, among which 7 categories compounds showed a significant increasing trend with the increase of soil pH, while the other 15 categories compounds showed the opposite trend. Based on the functional analysis of characteristic metabolites, this study found that with the increase of soil pH in tea rhizosphere, the diversity and number of soil microorganisms increased, and the cyclic ability of C and N of tea rhizosphere soil was enhanced, which in turn might lead to the enhancement of resistance of tea tree and promote the growth of tea tree.