Scanning of high-power laser beam on surface of martensitic stainless steel (SS420) has been studied, addressing the effect of scanning rate V on integrity modifications in the near-surface regions. Structural, compositional, and crystallographic characterizations revealed the presence of ablations, surface melting/resolidification, surface oxidations, and austenite (γ-phase) precipitations when V ≤ 20 mm/s. Melt pool (MP), heat affected zone (HEA), and base material have been clearly distinguished at the cross-section of the slow-scanned samples. Adjacent MPs partially overlapped when V = 5 mm/s. The γ-phase precipitations solely occurred in the MPs, i.e., of ~ 400 μm deep for V = 5 mm/s, while oxidations dominantly occurred in the surface regions of shallower than ~30 μm within the MPs. Compositional analysis revealed increased Cr-, Mn-, and Si-to-Fe ratios at the laser-scanned surface but absence of variations along the surface normal direction. Hardened surface has been achieved up to 805 HV, and the hardening monotonically decreased when moving deeper (i.e., ~1000 μm) into the base material. These observations shed new lights on surface engineering of metallic alloys via laser-based direct energy treatments.