This paper aims to cast light on the reasons that explain the shift of opinion—from scepticism to realism—concerning the reality of atoms and molecules in the beginning of the twentieth century, in light of Jean Perrin’s theoretical and experimental work on the Brownian movement. The story told has some rather interesting repercussions for the rationality of accepting the reality of explanatory posits. Section 2 presents the key philosophical debate concerning the role and status of explanatory hypotheses c. 1900, focusing on (...) the work of Duhem, Stallo, Ostwald, Poincaré and Boltzmann. Section 3 examines in detail Perrin’s theoretical account of the molecular origins of Brownian motion, reconstructs the structure and explains the strength of Perrin’s argument for the reality of molecules. Section 4 draws three important lessons for the current debate over scientific realism. (shrink)