A novel series of nanostructured catalysts composed of Al₂O₃ supported on a phosphorous (P) modified mesoporous carbon (ACP) derived from orange peel residues was formed. The formed, 1−7% (w/w) alumina/ACP, catalysts were investigated for conversion of methanol to dimethyl ether (DME) as a promising hydrogen carrier. The catalysts were characterized with a group of standard characterization techniques. Increasing of alumina loading caused remarkable structural and textural changes. Thus, new bands due to Al–O–P was detected by ATR−FTIR, which was confirmed by XPS as due to surface AlPO₄ species. However, no crystalline Al₂O₃ and/or AlPO₄ nanoparticles were detected by XRD or HRTEM. Meanwhile, the mesoporous surface texture was preserved. The loading of alumina led to increasing of Brønsted acidic sites population. The catalyst exhibited high conversion of methanol and complete …