Refining microstructure is an important issue for laser additive manufacturing (LAM) of titanium alloy. In the present work, the microstructures of LAM-fabricated Ti6Al4V alloy were refined using a low energy density with the combination of a small spot diameter, a low laser power, and a high scanning speed. The microstructure, hardness, wear performance, and molten pool thermal behavior of LAM-fabricated Ti6Al4V coatings were studied. The results show that the grain sizes of both prior β and α phases are strongly dependent on the cooling rate of the molten pool. The fine prior β grains and submicron-scale acicular α phases were obtained under a low energy density of 75 J mm−2 due to the high cooling rate of the molten pool. In addition, the as-fabricated Ti6Al4V sample with submicron-scale acicular α phase showed a very high hardness of 7.43 GPa, a high elastic modulus of 133.6 GPa, and a low coefficient of friction of 0.48. This work provides a good method for improving the microstructure and mechanical performance of LAM-fabricated Ti6Al4V alloy.