In situ TiC-reinforced composite surface layers (TRLs) were produced on a ductile cast iron substrate by laser surface alloying (LA) using pure Ti powder and mixtures of Ti-Cr and Ti-Mo powders. During LA with pure Ti, the intensity of fluid flow in the molten pool, which determines the TRL’s compositional uniformity, and thus Ti content in the alloyed zone, was directly affected by the fraction of synthesized TiC particles in the melt—with increasing the TiC fraction, the convection was gradually reduced. The introduction of additional Cr or Mo powders into the molten pool, due to their beneficial effect on the intensity of the molten pool convection, elevated the Ti concentration in the melt, and, thus, the TiC fraction in the TRL. It was found that the melt enrichment of Cr, in conjunction with non-equilibrium cooling conditions, suppressed the martensitic transformation of the matrix, which lowered the total hardness of the TRL. Moreover, the presence of Cr in the melt (~3 wt%) altered the growth morphology of the synthesized primary TiC precipitates compared with that obtained using pure Ti. The addition of Mo in the melt produced (Ti, Mo)C primary precipitates that exhibited a nonuniform Mo distribution (coring structure). The dissolution of Mo in the primary TiC precipitates did not affect its growth morphology.