Increasing food demand by the ever-growing population imposes an extra burden on the agricultural and food industries. Chemical-based pesticides, fungicides, fertilizers, and high-breeding crop varieties are typically employed to enhance crop productivity. Overexploitation of chemicals and their persistence in the environment, however, has detrimental effects on soil, water, and air which consequently disturb the food chain and the ecosystem. The lower aqueous solubility and higher hydrophobicity of agrochemicals, pesticides, metals, and hydrocarbons allow them to adhere to soil particles and, therefore, continue in the environment. Chemical pesticides, viz., organophosphate, organochlorine, and carbamate, are used regularly to protect agriculture produce. Hydrophobic pollutants strongly adhered to soil particles can be solubilized or desorbed through the usage of biosurfactant/s (BSs) or BS-producing and pesticide-degrading microorganisms. Among different types of BSs, rhamnolipids (RL), surfactin, mannosylerythritol lipids (MELs), and sophorolipids (SL) have been explored extensively due to their broad-spectrum antimicrobial activities against several phytopathogens. Different isoforms of lipopeptide, viz., iturin, fengycin, and surfactin, have also been reported against phytopathogens. The key role of BSs in designing and developing biopesticide formulations is to protect crops and our environment. Various functional properties such as wetting, spreading, penetration ability, and retention period are improved in surfactant-based formulations. This review emphasizes the use of diverse types of BSs and their source microorganisms to challenge phytopathogens. Extensive efforts seem to be focused on discovering the innovative antimicrobial potential of BSs to combat phytopathogens. We discussed the effectiveness of BSs in solubilizing pesticides to reduce their toxicity and contamination effects in the soil environment. Thus, we have shed some light on the use of BSs as an alternative to chemical pesticides and other agrochemicals as sparse literature discusses their interactions with pesticides. Life cycle assessment (LCA) and life cycle sustainability analysis (LCSA) quantifying their impact on human activities/interventions are also included. Nanoencapsulation of pesticide formulations is an innovative approach in minimizing pesticide doses and ultimately reducing their direct exposures to humans and animals. Some of the established big players and new entrants in the global BS market are providing promising solutions for agricultural practices. In conclusion, a better understanding of the role of BSs in pesticide solubilization and/or degradation by microorganisms represents a valuable approach to reducing their negative impact and maintaining sustainable agricultural practices.