The development of biodegradable plastic mulch films for use in agriculture has been ongoing for decades. These films consist of mixtures of polymers with various additives. As a result, their physical and chemical properties differ from those of the pure polymers often used for in vitro enzymatic and microbial degradation studies, raising questions about the biodegradation capability of mulch films. Currently, standards exist for the biodegradation of plastics in composting conditions but not in soil. Biodegradation in soil or compost depends on a complex synergy of biological and abiotic degradative processes. This review discusses the physicochemical and structural properties of biodegradable plastic mulches, examines their potential for on-site decomposition in light of site-to-site variance due to environmental and biological conditions, and considers the potential for long-term effects on agroecosystem sustainability and functionality.