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TiBCN films were deposited on Si(100) and cemented carbide substrates by using multi-cathodic arc ion plating in C2H2and N2atmosphere. Their structure and mechanical properties were studied systematically under different N2flow rates. The results showed that the TiBCN films were adhered well to the substrates. Rutherford backscattering spectroscopy was employed to determine the relative concentration of Ti, B, C and N in the films. The chemical bonding states of the films were explored by X-ray photoelectron spectroscopy, revealing the presence of bonds of TiN, Ti(C,N), BN, pure B, sp2C–C and sp3C–C, which changed with the N2flow rate. TiBCN films contain nanocrystals of TiN/TiCN and TiB2/Ti(B,C) embedded in an amorphous matrix consisting of amorphous BN and carbon at N2flow rate of up to 250 sccm.