In this study, ultraporous aluminas (UPA) were synthesized as new effective adsorbents for Remazol Brilliant Blue R (RBBR) removal from aqueous solutions. The UPA monoliths were grown via facile oxidation process, followed by isochronous annealing treatment in air at different temperatures, through which γ, θ, and α phase polycrystalline fibrous grains of UPA can be accordingly obtained. The experimental factors that affect the material adsorption performances including initial pH, contact time, and temperature were comprehensively studied by batch experiments. The RBBR adsorption isotherms of UPA(γ) and UPA(θ) powders were found almost identical, while UPA(α) powders showed low effectiveness. To obtain the desirable mechanical stability of the UPA monolith with considerable RBBR adsorption capacity, UPA(θ) powders were further studied. The UPA(θ) powders exhibited maximum RBBR adsorption at pH 2 due to the positively charged surface under acidic conditions. Compared with the Lagergren pseudo-first-order model, the pseudo-second-order model was found to explain the adsorption kinetics better. Despite the film diffusion dominating the adsorption process, the contributions of the intraparticle diffusion and chemical reactions were also found significant. The adsorption equilibrium data at different temperatures were fitted by the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D–R) isotherm models. The Langmuir model was found the most effective in the description of equilibrium data, and the maximum RBBR adsorption capacity retained by UPA(θ) powders was 122.55 mg·g−1 at 295 K. Thermodynamic parameters (ΔG0, ΔH0, and ΔS0) indicated the adsorption process was spontaneous and exothermic in nature.