This study examines the influence of micro-shot peening (MSP) on Monel 400 alloy, focusing on surface microstructural evolution and fluoride-induced corrosion behavior compared to its solution annealed (SAed) counterpart. MSP treatments were conducted at various surface coverages (100%, 200%, 500%, 1000%, 1500%, and 2000%). Characterization encompassed microhardness, surface roughness, grazing incidence x-ray diffraction (GI-XRD), field emission scanning electron microscopy (FE-SEM) with electron backscatter diffraction (EBSD), and transmission electron microscopy (TEM). With increasing the MSP coverage to 2000%, the surface crystallite size decreased from approximately ∼30 µm in the SAed sample to 60 nm. TEM analysis emphasized dislocation slip and formation of dislocation structures as the primary mechanisms for the grain refinement. However, the 2000% coverage exhibited microcrack formation, compromising its hydrofluoric (HF) corrosion resistance. Electrochemical tests revealed severe localized corrosion in all MSP-treated samples except the 1500% coverage, which exhibited a minimum passive current density of 0.2–1.0 µA/cm2. Inductively coupled plasma optical emission spectroscopy (ICP-OES) of immersion solutions showed lower copper and nickel ion concentrations (<150 ppm) in the 1500% MSP-treated sample, indicating its enhanced corrosion resistance. X-ray photoelectron spectroscopy (XPS) identified NiO, NiF2, CuO, CuF2, and Cu(OH)2 phases in SAed and 1500% MSPed samples, with a higher concentration of copper oxide (CuO) in the corrosion film of the 1500% MSP-treated sample, contributing to its superior corrosion resistance.