Slagging and fouling of boilers are typical technological problems in the combustion of solid fuels (especially coal and biomass). This study proposes a novel approach based on laser texturing of the near-surface layer of steel used to make heating surfaces of coal-fired boilers. This approach is aimed at improving the resistance of metal surfaces to slagging. The formation of slag deposits on the surfaces of AISI 310 S steel modified by laser radiation has been experimentally studied. The formation of slag melt was analyzed on the surface of modified and polished steel plates during heating to 1400 °C. High-temperature heating and interaction with slag led to a change in the chemical composition of the steel. A significant increase in the chromium content (up to 47%) of the steel surface and the transformation of its texture with the formation of grains up to 2.5 µm in size were established. Laser surface treatment significantly increased the resistance of the steel to such changes and also reduced the grain size to 1.5 µm. As a result of laser modification of surfaces, the temperature of slag formation shifts to higher values (higher by 60–75 °C compared to the unmodified polished surface). The anisotropic texture (cauliflower type) contributed to a decrease in the size of the slag spreading front, and also had by self-cleaning properties from the mineral melt. The latter allows to increase the reliability and energy efficiency of boiler equipment.