The substitution of biolubricant for mineral cutting fluids in aerospace material grinding is an inevitable development direction, under the requirements of the worldwide carbon emission strategy. However, serious tool wear and workpiece damage in difficult-to-machine material grinding challenges the availability of using biolubricants via minimum quantity lubrication. The primary cause for this condition is the unknown and complex influencing mechanisms of the biolubricant physicochemical properties on grindability. In this review, a comparative assessment of grindability is performed using titanium alloy, nickel-based alloy, and high-strength steel. Firstly, this work considers the physicochemical properties as the main factors, and the antifriction and heat dissipation behaviours of biolubricant in a high temperature and pressure interface are comprehensively analysed. Secondly, the comparative assessment of force, temperature, wheel wear and workpiece surface for titanium alloy, nickel-based alloy, and high-strength steel confirms that biolubricant is a potential replacement of traditional cutting fluids because of its improved lubrication and cooling performance. High-viscosity biolubricant and nano-enhancers with high thermal conductivity are recommended for titanium alloy to solve the burn puzzle of the workpiece. Biolubricant with high viscosity and high fatty acid saturation characteristics should be used to overcome the bottleneck of wheel wear and nickel-based alloy surface burn. The nano-enhancers with high hardness and spherical characteristics are better choices. Furthermore, a different option is available for high-strength steel grinding, which needs low-viscosity biolubricant to address the debris breaking difficulty and wheel clogging. Finally, the current challenges and potential methods are proposed to promote the application of biolubricant.