Effectiveness of steam explosion (SE) pretreatment for deconstructing the complex structural carbohydrates (SC) and lignin recalcitrance properties of rice straw (RS) for conjunctive improvement of biofuel yield and waste valorization was evaluated. This work exhibited successful pretreatment of RS at a different pressure (1.2, 1.5, and 1.8 MPa) and retention (3, 6, 9, and 12 min) for enhancement of SC contribution to biomethane production. Regression analysis demonstrated that SE pretreatment efficiency improved at high-temperature and short-retention time for biodegradation of RS. Maximum cumulative methane yield (EMY) achieved 254.8 mL/gvs at 1.2 MPa (3 min) of SE-treated RS with 62.7% of very significant improvement compared with untreated RS (156.6 mL/gvs). Furthermore, solid fraction of xylose, arabinose, cellobiose, glucose, and acid-soluble lignin in SE-treated RS of 1.2 MPa (3 min) were biodegraded by 27.4%, 46.4%, 100%, 48.8%, and 14.1%, respectively, after anaerobic digestion. Therefore, SE pretreatment was an encouraging approach for enhancing SC conversion to biomethane and waste resource to circular economy.