Aligned carbon nanofibers and hollow carbon nanofibers were grown by MW ECR-CVD method using methane and argon mixture gas at the temperature of 550••. Carbon nanofibers and hollow carbon nanofibers were deposited perpendicularly on Si substrate and on Si substrate coated with Ni catalyst, respectively. Raman spectra of aligned carbon nanofibers and hollow carbon nanofibers showed new bands of 1340 and 1612 cm-1 of the first-order Raman scattering and 2660, 2940 and 3220 cm-1 of the second-order Raman scattering. The second-order Raman scattering bands were assigned to two overtone and one combination bands on the basis of a similar assignment of micro crystal graphite. Combination bands are intense unusually. Field emitter characteristics of the well-aligned carbon nanofibers and hollow carbon nanofiberswere investigated and the current densities were 7.25 mA/cm2 and 0.69 mA/cm2at 12.5 V/μm, respectively.