In order to promote the improvement of rural living environments, the treatment of rural domestic sewage has attracted much attention in China. Meanwhile, the rural regions’ sewage discharge standards are becoming increasingly stringent. However, the standard compliance rate of the total phosphorus (TP) is very low, and the TP has become the main limiting pollutant for the water pollutant discharge standards of rural domestic sewage treatment facilities. In this study, oyster shell waste was employed as a calcium source, and agricultural waste−rice husk was used as a carbon source to synthesize calcium-modified biochar adsorbent materials (Ca-BC) by a simple one-step pyrolysis method. The resultant Ca-BC adsorbent materials demonstrated efficient phosphate (P) adsorption from aqueous solutions over a wide pH range (3−11) and adsorption selectivity. Ca-BC’s adsorption capacity for P increased with the pyrolysis temperature, increasing from 700 °C to 900 °C, which was attributed to the higher specific surface area and calcium oxide content at higher pyrolysis temperatures. The Ca-BC sample, which was made from oyster shells and rice husks with a mass ratio of 2:1 and a pyrolysis temperature of 900 °C, had a maximum adsorption capacity of 196.2 mg/g. The Langmuir model and pseudo-second-order model were the best at describing the adsorption process, and the predominant sorption mechanism for P is the precipitation of calcium oxide or calcium hydroxide with phosphate to create hydroxyapatite. Ca-BC can effectively remove P from rural domestic sewage. The removal rate of the total phosphorus (TP) in rural domestic sewage is 93.9−99.4%. After the adsorption treatment, the discharge of the TP in the rural sewage met the second-grade (TP < 3 mg/L) or even the first-grade (TP < 2 mg/L) Discharge Standard of Water Pollutants for Centralized Rural Sewage Treatment Facilities (DB33/973-2021). This study provides an experimental basis for efficient P removal by Ca-BC adsorbent materials and suggests possible applications in rural domestic sewage.