Three-dimensional hollow hoya-like nickel phosphate (NiP) microspheres derived from nickel metal–organic frameworks (Ni-MOFs) are constructed and a series of calcinated temperatures are performed to investigate the temperature influence on the morphological and compositional evolutions, as well as electrochemical performance in detail. It is observed as-designed NiP calcinated at 450 °C is most beneficial for the enzymeless glucose sensor and supercapacitor applications outperforming its counterparts, delivering a noteworthy sensitivity (1373.7 A mM−1 cm−2) with a low detection limit of 160 nM, and satisfactory results in real human serum sample when utilized as a glucose sensor, while attaining a high specific capacity 1625F g−1 (1 A g−1) and exceptional rate performance (remaining 75.9% of its initial capacitance at 20 A g−1) for supercapacitor application. Here, the open structure configuration, interconnected flower-like nanosheets and amorphous state owing to NiP-450, like blooming “flowers”, make the active materials employed efficiently, ion/charge transferred rapidly and volume deformation decreased, significantly enhanced electrochemical properties, suggesting its competitive advantages in biosensor and supercapacitor research fields and capability as a promising candidate in future practical applications.