Uniformly sized microspheres tangled with cup-stacked carbon nanofibers (CSCNFs) were directly synthesized by the pyrolysis of poly(ethylene glycol) (PEG) with a nickel catalyst. A PEG/Ni membrane was prepared on a silicon wafer surface by heating it to 750 degrees C at a heating rate of 15 degrees C min(-1). The wafer was heated to a temperature of 400 degrees C and was held at that temperature for 1 h before raising the temperature to 750 degrees C for 10 min to form the CSCNF microspheres. The final CSCNF microspheres and the intermediates were evaluated using scanning electron microscopy, transmission electron microscopy, X-ray diffractometry, and Raman spectroscopy to elucidate the growth mechanism. Furthermore, the CSCNF microspheres were successfully dispersed and maintained their spherical shape in an aqueous solution containing 0.5% Nafion. The CSCNF microspheres have the potential to work as a sophisticated carrier with high adsorption and fast electron-transfer exchange properties based on the graphene edges of the nanofiber surface.