Solid-state thermochromic materials undergo semiconductor to metal transitions at a ‘critical temperature’, Tc. This review begins by describing the phenomenon of thermochromism, whereby the optical properties of a material change reversibly as a result of a change in temperature. The various different types of thermochromism will be introduced with a focus on the thermochromism exhibited by solid-state materials. The fundamental chemical principles that describe the electronic structure and properties of solids, and the chronological developments in the theory behind the thermochromic transitions (such as, the effects of electron-electron interactions and structural phase changes due to lattice distortions) that led to the discovery of the semiconductor-to-metal transition, are presented. An extensive discussion of vanadium and titanium oxides is presented with a particular focus on vanadium (IV) oxide since its transition temperature is closest to room temperature. Observations and current understanding of the nature of the semiconductor-to-metal transition exhibited by these materials is detailed. The possibility of fine-tuning the transition temperature by introducing various dopants into the vanadium (IV) oxide lattice is examined and the effects of dopant charge and size is examined. Solid-state thermochromic materials may be exploited in areas such as microelectronics, data storage, or intelligent architectural glazing, thus are required to be synthesised as thin films for use in such applications. The numerous synthetic techniques (PVD, sol-gel method, PLD, CVD, APCVD and AACVD), for making metal oxide thermochromic thin films are described in reference to the production of vanadium (IV) oxide and compared. Finally rare earth nickelates exhibiting thermochromism are described.