We demonstrate the synthesis of calcium phophate fluoride hybrid hollow spheres with well controlled size and morphology through self assembly process using Poly (ethylene oxide)–poly (propylene oxide)–poly (ethylene oxide) triblock copolymer (Pluronic P123) as the template. The diameter and the shell thickness of the hollow spheres is typically in the range of 100–600nm and 150–200nm respectively. Scanning electron microscope (SEM), Energy dispersive X-ray spectrometer (EDX), Transmission electron microscopy (TEM) and N 2 adsorption–desorption analyses confirmed that well organized hollow spherical structures have been developed. The formation mechanism is attributed to the change in the hydrophobic–hydrophilic balance by the fluoride ions (F − ). Our result provides a simple route for the synthesis of inorganic hollow spheres by templating strategies.