Laser-assisted diamond cutting is a promising process for machining hard and brittle materials. A deep knowledge of material removal mechanism and attainable surface integrity are crucial to the development of this new technique. This paper focuses on the application of laser-assisted diamond cutting to single crystal silicon to investigate key characteristics of this process. The influence of laser power on the ductile machinability of single crystal silicon, in terms of the critical depth of cut for ductile-brittle transition in laser-assisted diamond cutting, is investigated quantitatively using a plunge-cut method. The experimental results reveal that this process can enhance the silicon’s ductility and machinability. The critical depth of cut has been increased by up to 330% with laser assistance, and its degree generally increases with the increase of laser power. The cross-sectional transmission electron microscope observation results indicate that laser-assisted diamond cutting is able to realize the subsurface damage free processing of single crystal silicon. In order to verify the ability of the laser-assisted diamond cutting to improve the surface quality, the face turning tests are also carried out. A significant improvement of surface quality has been obtained by laser-assisted diamond cutting: Sz (maximum height) has been reduced by 85% and Sa (arithmetical mean height) has been reduced by 45%.