Biodegradable mulches are considered a promising alternative to polyethylene-based, nonbiodegradable mulch for sustainable agriculture. In the present study, a bioactive 2-methyl-4- cholorophenoxyacetic acid/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (MCPA-PHBV) conjugate blended with biodegradable poly(butylene adipate-co-terephthalate/polylactide (PBAT/PLA) was developed and used as mulch under controlled condition greenhouse pot experiment with fava bean (Vicia faba) as the nontarget crop species. The objectives were to examine the effectiveness of sustained-release of MCPA herbicide from biodegradable mulch for broadleaf weed suppression and to assess any adverse effects of the herbicide on the nontarget species (fava bean). The energy-dispersive X-ray spectroscopy analysis (EDS) suggests that a substantial quantity of the herbicide was released from the biodegradable mulch which effectively killed the broadleaf weed species even at 1% MCPA concentration. However, the higher concentrations of the herbicide adversely affected several physiological parameters of fava bean growth and development. Stomatal conductance decreased, while leaf temperature subsequently rose (at MCPA concentrations 5, 7.5, and 10%). The quantum yield of the Photosystem II (PSII) indicates that the photosynthetic efficiency was also restricted at concentrations 7.5% and 10%. Evidently, this slow-release herbicide system worked efficiently for broadleaf weed control but at higher concentrations, resulted in adverse physiological effects on the nontarget crop species. This study has demonstrated that biodegradable mulches containing MCPA herbicide are able to effectively inhibit the growth of broad leaf weed species and may be of potential importance in a wide variety of horticultural and agricultural applications.