In this investigation, synthesis of a surface-functionalized chitosan known as amino-rich chitosan (ARCH) was achieved by successful modification of chitosan by polyethyleneimine (PEI). The synthesized ARCH was characterized by a specific surface area of 8.35 m2 g−1 and a microporous structure, with pore sizes predominantly under 25 nm. The Zeta potential of ARCH maintained a strong positive charge across a wide pH range of 3–11. These characteristics contribute to its high adsorption efficiency in aqueous solutions, demonstrated by its application in removing various anionic dyes, including erioglaucine disodium salt (EDS), methyl orange (MO), amaranth (ART), tartrazine (TTZ), and hexavalent chromium ions (Cr(VI)). The adsorption capacities (Qe) for these contaminants were measured at 1301.15 mg g−1 for EDS, 1025.45 mg g−1 for MO, 940.72 mg g−1 for ART, 732.96 mg g−1 for TTZ, and 350.15 mg g−1 for Cr(VI). A significant observation was the rapid attainment of adsorption equilibrium, occurring within 10 min for ARCH. The adsorption behavior was well-described by the Pseudo-second-order and Langmuir models. Thermodynamic studies indicated that the adsorption process is spontaneous and endothermic in nature. Additionally, an increase in temperature was found to enhance the adsorption capacity of ARCH. The material demonstrated robust stability and selective adsorption capabilities in varied conditions, including different organic compounds, pH environments, sodium salt presence, and in the face of interfering ions. After five cycles of adsorption, ARCH maintained about 60% of its initial adsorption capacity. Due to its efficient adsorption performance, simple synthesis process, low biological toxicity, and cost-effectiveness, ARCH is a promising candidate for future water treatment technologies.