In this research, use of aluminum oxide nano-particles (Al2O3-NPs) as a catalyst and co-catalyst in the wrinkle-resistant finishing of cotton fabric with 1,2,3,4-butanetetracarboxylic acid (BTCA), was investigated. For this, cotton fabrics were cross-linked with BTCA catalyzed by Al2O3-NPs or sodium hypophosphite (SHP) in the presence of Al2O3-NPs as the co-catalyst. Surface morphology and chemical composition of the treated fabrics beside the fabric properties, such as wrinkle resistance, flame retardancy, yellowing, and air permeability, were also evaluated. Scanning electron microscope and energy-dispersive X-ray microanalysis proved the presence of Al2O3-NPs on the fabric structure. The cross-linking of the fabrics with BTCA catalyzed by Al2O3-NPs or SHP was identified by Fourier transform infrared spectroscopy. The fabric test results indicated that the Al2O3-NPs co-catalyst could act as a multifunctional finishing material. The flame retardant property of the fabric, besides wrinkle resistance, was improved. It was also concluded that Al2O3-NPs could enhance the finishing performance and minimize the side effect of SHP.