apid development in industrialization and urbanization causes serious environmental issues, of which acid rain is one of the quintessential hazards, negatively affecting soil ecology. Liming has been investigated for a long time as the most effective amendment to alter the adverse effects of soil acidity resulting from acid rain. Herein, this study tested the biochar produced from invasive plants as an alternative amendment and hypothesized that biochar can maintain better availability of macronutrients under acid rain than liming by improving soil chemical and biological properties. Therefore, a pot experiment was conducted to compare the effects of lime and biochar at two rates (1% and 3%) on soil available nitrogen (N), phosphorous (P) and potassium (K) under simulated acid rain of two pH levels (4.5: pH4.5 and 2.5: pH2.5) as compared with tap water ( pH7.1) as a control treatment. Biochar was produced using different invasive plants, including Blackjack (Biden Pilosa), Wedelia (Wedelia trilobata) and Bitter Vine (Mikania micrantha Kunth). Liming decreased the availability of soil N, P, and K by 36.3% as compared with the control due to the great increment in soil pH and exchangeable calcium ( Ca2+) by 59% and 16-fold, respectively. Moreover, liming reduced the alpha diversity of soil bacteria and fungi by 27% and 11%, respectively. In contrast, biochar at different types and rates resulted in a fourfold increment in the available N, P, and K as an average under acid rain ( pH4.5 and pH2.5) owing to maintaining a neutral pH (6.5–7), which is the most favorable level for soil microbial and enzymatic activites, and the bioavailability of soil nutrients. Furthermore, biochar caused balanced increments in Ca2+ by threefold, cation exchange capacity by 45%, urease activity by 16%, and fungal diversity by 10%, while having a slight reduction in bacterial diversity by 2.5%. Based on the path, correlation, and principal component analyses, the exchangeable aluminum was a moderator for the reductions in macronutrients’ availability under acid rain, which decreased by 40% and 35% under liming and biochar, respectively. This study strongly recommended the use of biochar from invasive plants instead of lime for sustainable improvements in soil properties under acid rain.