Organic dye-containing wastewater has become an increasingly serious environmental problem due to the rapid development of the printing and dyeing industry. Hydrogel is a promising adsorbent for organic dyes because of its unique three-dimension network structure and versatile functional groups. Though many efforts have been made in hydrogel adsorbents recently, there is still a critical challenge to fabricate hydrogel adsorbent with high adsorption capacity and high efficiency at the same time. To address this concern, we developed a calcium hydroxide nano-spherulites/poly(acrylic acid -[2-(Methacryloxy)ethyl]trimethyl ammonium chloride) hydrogel adsorbent with novel villi-like structure. The hydrogels were prepared through a simple free radical copolymerization method using calcium hydroxide nano-spherulites as crosslinker. The resultant hydrogel adsorbents showed a maximum adsorption capacity of 2249 mg/g in a 400 mg/L methylene blue solution and a high removal ratio of 98% in 1 h for a 50 mg/L methylene blue solution. In addition, the adsorption behaviors of our hydrogel adsorbents could be well described by pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Furthermore, this kind of hydrogel adsorbent showed selective adsorption behavior for methylene blue. Altogether, the hydrogel adsorbent developed in this work has a high capacity and high efficiency in organic dye removing and promised a great potential in wastewater treatment application.