Comb-like Cd(x)Zn(1-x)S nanostructures have been synthesized by one-step metallo-organic chemical vapor deposition (MOCVD). The microstructure and composition were characterized by analytical transmission electron microscopy (TEM). The ribbon of the comb-like structure is along [2-1-10] (the a-axis), and the nanotips are along [0001] (the c-axis). The atomic location by channeling-enhanced microanalysis (ALCHEMI) technique was used to determine the polarity of the crystal via electron energy-loss spectroscopy (EELS). The thickness dependence, delocalization and beam convergent effect are discussed here. The investigations reveal that the growth mechanism is consistent with the asymmetric growth.