Pulsed plasma treatment was applied for surface modification and laminated coating deposition on 14.5wt%-Cr cast iron. The scopes of the research were: (a) to obtain a microstructure gradient, (b) to study the relationship between cathode material and coating layer microstructure/hardness, and (c) to improve coating quality by applying post-deposition heat treatment. An electrothermal axial plasma accelerator with a gas-dynamic working regime was used as plasma source (4.0 kV, 10 kA). The layered structure was obtained by alternation of the cathode material (T1-18 wt% W high speed steel and 28 wt% Cr-cast iron).