Human population growth requires higher agricultural productivity, a challenge that all nations face. Agrochemicals, such as fertilizers, pesticides, fungicides, and plant growth hormones, are used in significant quantities in agriculture to boost productivity and eliminate major threats, including insects, pests, pathogenic organisms, and weeds, as well as other diseases. The lower water solubility and higher hydrophobicity of these substances enable them to persist in soil and subsequently diffuse into water bodies. Overuse of these agrochemicals and their persistence in the environment harm the food chain, ecosystem, and consumers. Therefore, the use of green compounds, meaning eco-friendly or bio-based agrochemicals, which are integral to sustainable agriculture practices, is clearly essential in the current era. Thanks to low toxicity, exceptional environmental stability, and eco-friendliness, biosurfactants and the microorganisms that produce them are gaining popularity nowadays. They augment the efficacy of pesticides and fertilizers while mitigating ecological impacts by enhancing nutrient bioavailability in soil and promoting the desorption and remediation of pesticides, attributable to their diverse functional properties, including wetting, spreading, and penetration capabilities. According to literature, some biosurfactants, including surfactin, rhamnolipids (RL), mannosylerythritol lipids (MELs), and sophorolipids (SL), exhibit broad-spectrum antibacterial activity against a variety of phytopathogens. Thus, the biosurfactants represent a sustainable alternative to conventional agrochemicals, which brings the global efforts in line to reduce environmental pollution and encourage sustainable/green agriculture. However, constant research/exploration, technological innovations, and regulatory support are crucial for translating their laboratory potential into large-scale agricultural applications. This chapter covers the organisms that produce biosurfactants; characteristics of biosurfactants; formulations of biosurfactant-based agrochemicals; their advantageous effects on the environment, humans, and cultivated crops—including plant growth promotion, challenges to phytopathogens, efficacy in solubilizing agrochemicals to mitigate toxicity, and minimal dosage with lesser side effects to ecosystems—and their applications within the agricultural sector. Also, a few statistics related to biosurfactant-based agrochemicals shall be discussed.