In comparison with neutral covalent organic frameworks (COFs), few studies have been conducted on the synthesis and applications of ionic COFs. In this work, a novel cationic covalent organic framework (CCOF) with high porosity and crystallinity is synthesized by reacting ionic tris-aldehyde with 4,4’-oxydianiline through the catalyst-free Schiff’s base reaction. The structural properties of cationic COF were characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), highresolution transmission electron microscopy (HR-TEM), Atomic force microscopy (AFM), thermogravimetric analysis (TGA), and Brunauer-Emmett-Teller (BET) surface area analysis. Application of this cationic COF as an adsorbent for selective removal of anionic dyes with sustainability concerns is investigated. The synthesized cationic COF exhibited good removal efficiency (95%) for methyl orange. The adsorption process was exothermic and fitted perfectly with the Langmuir isotherm with a high correlation coefficient (R2 ¼ 0.9737) and maximum adsorption capacity (196.08 mg/g) and pseudo-second-order kinetic model.