This chapter presents a novel method for analysis and optimization of the in-situ formation of TiC-reinforced composite surface layers (TRL) on a ductile cast iron substrate during the laser surface alloying process, combining the experimental approach with the computational thermodynamics. The microstructure of the TRLs has been assessed by light optical microscopy, scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction. The results of thermodynamic calculations with the Scheil-Gulliver model showed a good agreement with the experimental results, indicating that the actual solidification path for the analyzed Fe-C-Si-Ti alloy systems under the investigated range of laser processing conditions is close to the Scheil-Gulliver assumption.