Co3O4 microspheres with free-standing or bundled nanofibers (NFs) were fabricated for use as a platform for non-enzymatic glucose sensing. The sensor based on free-standing Co3O4 NFs displays enhanced sensitivity (1440 μA mM(-1) cm(-2)), a wider linear range (0.005-12 mM) and superior selectivity. The application of this glucose sensor in human blood serum has also been demonstrated successfully.