A water-insoluble picket-fence porphyrin was first assembled on nitrogen-doped multiwalled carbon nanotubes (CN(x) MWNTs) through Fe--N coordination for highly efficient catalysis and biosensing. Scanning electron micrographs, Raman spectra, X-ray photoelectron spectra, UV/Vis absorption spectra, and electrochemical impedance spectra were employed to characterize this novel nanocomposite. By using electrochemical methods on the porphyrin at low potential in neutral aqueous solution, the presence of CN(x) MWNTs led to the direct formation of a high-valent iron(IV)-porphyrin unit, which produced excellent catalytic activity toward the oxidation of sulfite ions. By using sulfite ions, a widely used versatile additive and preservative in the food and beverage industries, as a model, a highly sensitive amperometric biosensor was proposed. The biosensor showed a linear range of four orders of magnitude from 8.0x10(-7) to 4.9x10(-3) mol L(-1) and a detection limit of 3.5x10(-7) mol L(-1) due to the highly efficient catalysis of the nanocomposite. The designed platform and method had good analytical performance and could be successfully applied in the determination of sulfite ions in beverages. The direct noncovalent assembly of porphyrin on CN(x) MWNTs provided a facile way to design novel biofunctional materials for biosensing and photovoltaic devices.