Two well-defined CoFe bimetal oxides are prepared from Prussian blue analogues (PBAs) as precursors with designable structures, which are further explored for phosphate removal. A speed-controlled coordination strategy is used to fabricate two CoFe PBA microcrystals with different morphologies, then two regular CoFe oxides are obtained via an intermediate-temperature calcination. CoFeS, a slow-speed coordination product with truncated microcube structure, contains less coordinated water and Fe3+ in its framework, but can create more mesopores and Fe3+ in its oxidative product of CoFeST300. CoFeST300 has been demonstrated to have higher adsorption capacity and affinity for phosphate adsorption compared to that of the fast-speed coordination product, due to its more Fe3+ as effective adsorption sites via ligand exchange. Besides, the inner-sphere complexation mechanism makes CoFeST300 high selectivity for phosphate removal compared to other co-existing anions. The application performance of CoFeST300 is examined by multiple continuous treatment of actual sewage, and the result of all effluent concentrations below 0.5 mg P/L verifies a promising potential of the fabricated adsorbent for phosphorus removal. Thus, design or regulation of the precursors is an efficiency method to fabricate an ideal metal oxide for phosphate adsorption.