The wear behavior of Ni-based single crystal (NBSC) superalloy SRR99 fabricated by laser-directed energy deposition (LDED) is investigated and compared with that of its cast counterpart. While γ’ precipitate size in the latter is > 400 nm, that in the former is an order of magnitude lower. Dry sliding wear tests reveal that the wear rate and coefficient of friction of the LDED alloy are 75 % and 20 % lower than that of its cast counterpart, respectively. Detailed transmission electron microscopy investigation of the wear-tested cast alloy indicates that there is orientation change and formation of nanoscale grains only at the top layer of the worn surface, whereas regions below undergo moderate plastic deformation via dislocation slip. In contrast, the sub-surface of the worn LDED alloy has a graded microstructure, with a composite of NiO/γ-Ni on the top, γ’ free nano-grains in the middle, and a highly deformed nanoscale layer at the bottom. The improved wear behavior of the LDED alloy is attributed to its higher dislocation density, finer γ’ precipitates, and the formation of this graded microstructure. Finally, a detailed description of mechanisms that lead to the formation of this unique graded microstructure is provided.