The emission of volatile organic compounds (VOCs) has resulted in increasingly severe harm to the environment and human health. In recent years, biological methods have become the preferred technology for VOC removal due to their environmental friendliness and economic advantages. Based on the theory of bibliometrics, this study analyzed research articles and reviews on biological methods for VOC removal published in the Web of Science Core Collection (WOSCC) database from 1966 to 2021. The knowledge map visualization software CiteSpace was utilized to analyze research progress in different countries, co-citation clustering, co-citation bursts, and keyword clustering in the literature data. The results indicated that early research on VOC biological treatment focused on the removal of odorous gases and single components of volatile organic waste gases. Subsequently, benzene contents (BTEX), hydrophobic VOCs, and multi-component VOCs have gradually become the focus of research. In recent years, improving VOC removal efficiency by studying packing materials and microbial communities has become an important research topic both domestically and internationally. Future research should focus on continuously improving the performance of reactors, developing novel reactors, and investigating technologies for treating complex and recalcitrant VOCs.