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Carbon nitride films have been synthesized in a wide range of biases from 0 to -900 V by vacuum cathodic arc method. The N content was about 12.0～22.0 at. Pct. Upon increasing the biases from 0 to -100 V, the N content increased from 15.0 to 22.0 at. Pct which could be attributed to the knot-on effect. While the further increasing biases led to the gradual falling of the N content to 12.0 at. Pct at -900 V due to the enhancement of the sputtering effect. Below -200 V, with the increasing biases the sp2C fraction in the films decreased, as a result of which the I(D)/I(G) fell in the Raman spectra and the sp peaks also showed the decreasing tendency relative to the s peaks in the VBXPS (valence band X-ray photoelectron spectroscopy). While above -200 V, the sp2C fraction increased and the films became graphitinized gradually, accompanying which theI(D)/I(G) rose from -200 V to -300 V and the Raman spectra even showed the graphite characteristic above -300 V and the sp peaks rose again relative to the s peak. The carbon nitride films mainly consist of three types of bonding: CC, sp2CN and sp3CN bonds. In the first stage the sp3CN relative ratio rises and falls in the second stage, which corresponded well with the variation of the sp2C in the films. The subplantation mechanism resulting from the effect of ion energy played an important role in decidingthe variation of the microstructure of the carbon nitride films.