In this work, the synthesis of the Li₂TiSiO₅ photoluminescent compound, obtained from a stoichiometric mixture of Li₂CO₃, SiO₂ and TiO₂ nanoparticles, was investigated by two different routes named route I (melting and quenching) and route II (solid-state reaction). In the route I, the raw materials were melted (1550 °C/2 h) and cooled into water. Subsequently, the solidified product was milled (30 min) in a high-energy mill. In the route II, the raw materials were directly milled (10 min). The obtained powders, from both routes, were heat treated at different temperatures (900–1000 °C/60 min) and then subjected to crystallographic (XRD) and thermal (DSC) analyses in order to investigate the resulting structure and the associated physical–chemical reactions. The results showed that it is possible to obtain the Li₂TiSiO₅ compound from both synthesis routes but, apparently, the route I seems to be more appropriated to obtain the Li₂TiSiO₅ compound and to demonstrate the photoluminescence phenomena with and even without thermal treatment.