Non-conventional materials are the emerging demand for machine tool structures, while smooth operations have been hindered due to vibration and thermal deformation of machine tool structures, especially in precision machining. This paper attempts to review and summarize the key developments in the area of non-conventional materials for machine tool structures over the last two decades. Many beneficial properties of the machine tool structural materials are compared with the conventional cast iron. To support the ever-rising working speeds made possible by the development of tools and machining processes, the increasing requirements concerning the surface finish of the machined workpieces and the fabrication cost of the machine tool structures exerted the impetus to find alternatives to cast iron. Based on the results of previous studies, composite materials may be the paragon.