Depth profile analysis was performed using two mass spectrometry analytical techniques applying argon ion sputtering—secondary ion mass spectrometry (SIMS) and glow discharge mass spectrometry (GDMS). 150 nm Ni/20 nm Ti/4H-SiC structure was prepared by evaporation coating with titanium and nickel. The structure was analysed as prepared and annealed in 600°C in dry N2. Obtained results allow monitoring several processes present during annealing of Ni/Ti/SiC structures. These are nickel diffusion and its reaction with SiC leading to formation of Ni2Si, precipitation of carbon and segregation of titanium. Results are also used for comparison of the two analytical techniques used. The techniques base on different ionisation mechanisms. In SIMS, secondary ions are formed at the bombarded surface during ion sputtering process in ultra-high vacuum environment, while in GDMS, ionisation occurs in glow discharge above the eroded surface in low vacuum.