Aluminium nitride (AlN) materials are widely used in heat-dissipation substrates and electronic device packages. However, the application of aluminium nitride ceramics is hindered by the obvious anisotropy and high brittleness of its crystals, leading to poor material surface integrity and high grinding force. With the rapid development of microelectronics, the requirements for the material’s dimensional accuracy, machining efficiency, and surface accuracy are increasing. Therefore, a new machining process is proposed, combining laser and ultrasonic vibration with grinding. The laser–ultrasonic-assisted grinding (LUAG) of aluminium nitride is simulated by molecular dynamics (MD). Meanwhile, the effects of different processing techniques on grinding force, stress distribution, matrix damage mechanism, and subsurface damage depth are systematically investigated and verified by experiments. The results show that laser–ultrasonic-assisted grinding produces 50% lower grinding forces compared to traditional grinding (TG). The microhardness of AlN can reach more than 1200 HV, and the coefficient of friction and wear is reduced by 42.6%. The dislocation lines of the AlN substrate under this process are short but interlaced, making the material prone to phase transformation. Moreover, the subsurface damage depth is low, realising the substrate’s material hardening and wear resistance. These studies not only enhance the comprehension of material build-up and stress damage under the synergistic impact of laser, ultrasonic, and abrasive processing but also indicate that the proposed method can facilitate and realise high-performance machining of aluminium nitride substrate surfaces. Abstract Aluminium nitride (AlN) materials are widely used in heat-dissipation substrates and electronic device packages. However, the application of aluminium nitride ceramics is hindered by the obvious anisotropy and high brittleness of its crystals, leading to poor material surface integrity and high grinding force. With the rapid development of microelectronics, the requirements for the material’s dimensional accuracy, machining efficiency, and surface accuracy are increasing. Therefore, a new machining process is proposed, combining laser and ultrasonic vibration with grinding. The laser–ultrasonic-assisted grinding (LUAG) of aluminium nitride is simulated by molecular dynamics (MD). Meanwhile, the effects of different processing techniques on grinding force, stress distribution, matrix damage mechanism, and subsurface damage depth are systematically investigated and verified by experiments. The results show that laser–ultrasonic-assisted grinding produces 50% lower grinding forces compared to traditional grinding (TG). The microhardness of AlN can reach more than 1200 HV, and the coefficient of friction and wear is reduced by 42.6%. The dislocation lines of the AlN substrate under this process are short but interlaced, making the material prone to phase transformation. Moreover, the subsurface damage depth is low, realising the substrate’s material hardening and wear resistance. These studies not only enhance the comprehension of material build-up and stress damage under the synergistic impact of laser, ultrasonic, and abrasive processing but also indicate that the proposed method can facilitate and realise high-performance machining of aluminium nitride substrate surfaces. Keywords: aluminium nitride; laser–ultrasonic-assisted grinding; molecular dynamics; surface hardness; grinding force