In the present paper, the structure of electric arc coatings modified with nanodispersed titanium carbonitride additives on low-carbon pipe steel is studied using optical, scanning tunneling, and transmission electron microscopy. The obtained “substrate-modified surface” compositions are tested for fracture toughness, and the derived test results are compared with the data for the compositions formed using commercial electrodes. It is found that the introduction of titanium carbonitride nanoparticles with the estimated content from 0.15 to 1 wt% refines the ferrite–pearlite structure. Scanning tunneling microscopy reveals acicular and lamellar structures in local regions of ferrite grains, which, by morphological features, are identified as lower bainite and acicular ferrite. It is concluded that the increase in fracture toughness of the “substrate-modified surface” composition is of a complex nature. First of all, this increase is associated with grain refinement, while the formation of intermediate transformation structures plays a secondary role.