Abstract: Much has been said about the accuracy of the famous predictions of the Russian chemist Dmitrii Ivanovich Mendeleev, but far less has been written on how he made his predictions. Here we offer an explanation on how Mendeleev used his periodic system to predict both physical and chemical properties of little-known and entirely unknown chemical elements. We argue that there seems to be compelling evidence in favour of Mendeleev genuinely relying on his periodic system in the course of issuing his predictions—a point recently contested by Woody (in: Soler, Zwart, Lynch, Israel-Jost (eds) Science after the practice turn in the philosophy, history, and social studies of science, Routledge, Abington, 2014). In particular, by using the known properties of a number of near neighbours of the three entirely unknown elements (the so-called eka-elements), we seek to show how the very format of his table enabled it to function as a powerful tool for Mendeleev in arriving at his predicted values. We suggest that Mendeleev’s use of the periodic system in making his prediction gives an illuminative example of what Woody calls “theoretical practices” in science.