Copper hydroxyphosphate, Cu2(OH)PO4, with six hierarchical architectures was successfully synthesized through a hydrothermal route. The resulting hierarchical superstructures were characterized using powder X-ray diffraction and scanning electron microscopy. In this hydrothermal process, the morphology of copper hydroxyphosphate changed drastically with the addition of different amounts of alcohol (ethanol, n-propanol, or ethylene glycol) as solvent. A possible mechanism for the formation of these copper hydroxyphosphate hierarchical superstructures is proposed. This approach provides a facile strategy to synthesize copper hydroxyphosphate crystals with unique morphologies and complex architectures. This binary reaction medium (alcohol and water) could provide an alternative and versatile strategy for controlling inorganic microcrystals by manipulating the supersaturation of the growing solution.