This study evaluates the effect of commercial biological and chemical ensiling additives on improving the anaerobic digestibility of sugarcane bagasse, a significant agro-industrial residue. Seven additives, representing homofermentative, heterofermentative, acid-based, and yeast-based pathways, were tested at ambient temperature under anaerobic conditions and compared with untreated and fresh bagasse. The ensiling process significantly modified substrate composition, reducing water-soluble carbohydrates while increasing lactic and acetic acids and alcohol concentrations, thereby influencing methane yield and energy recovery. The most effective ensiling strategy, SILASIL ENERGY. XD (a blend of homo- and hetero-fermentative bacteria), increased methane productivity to 74.53 L/kg, compared to 61.12 L/kg for untreated ensiled bagasse. On organic total solids basis, this represented a 55.37% increase over untreated ensiled bagasse and 27.77% more than fresh bagasse, demonstrating improved digestibility and conversion efficiency. Methane energy values confirmed that effective ensiling strategies could enhance energy recovery, potentially increasing by up to 28.30%, despite some dry matter losses during storage. These findings highlight ensiling as a practical, cost-effective strategy for enhancing methane potential and supporting sustainable waste-to-energy utilization of sugarcane bagasse.