To clarify the microstructure evolution, defect characteristics and suppression methods for multilayer cladding by laser melting deposition (LMD), experimental research on multilayer LMD of Fe-Cr alloy with different laser energy densities was carried out. The phase composition and the evolution rules of the phase during the melting-solidification process were analyzed. The crystal growth trend, dendritic transition and dendrite spacing of multilayer Fe-Cr coatings were investigated. The formation mechanism of crack, porosity and surface spheroidization defects were revealed, the effects of laser energy densities on the defects were analyzed, and the defect suppression methods were proposed and verified. The results showed that the primary and secondary remelting zones of multilayer Fe-Cr coatings were fine equiaxed dendrites and irregular cellular structures, respectively. When the laser energy density increased from 22.74 J/mm2 to 55.70 J/mm2, the dendrite spacing increased gradually, and the porosity and spheroidization defects showed a trend of improvement and then deterioration. The cracks were considered cold cracks with transgranular characteristics. Meanwhile, when the residual stress exceeded the theoretical fracture strength of 1.6 GPa, the multilayer cladding experienced brittle fracture and formed cracks. Selecting an appropriate laser energy density and preheating treatment can effectively improve the forming quality and inhibit the formation of defects.