In this study, we investigated ontogenetic and sexual changes of the brain scaling as well as the scaling and the relative size of six major brain areas in the small-spotted catshark Scyliorhinus canicula from the Mediterranean Sea. The brain somatic index (0.31–1.25%) did not differ significantly between sexes but was significantly affected by size with smaller specimens exhibiting higher values. Brain growth exhibited negative allometry (allometric coefficient 0.634), not affected by sex or maturity status. The brain growth rate was found to be higher compared with a previous study from the Atlantic Ocean. Regarding the scaling of the brain areas, the olfactory bulbs scaled with positive allometry, the telencephalon and the diencephalon scaled with the same rate of negative allometry, the mesencephalon exhibited even higher negative allometry, while the cerebellum and the medulla oblongata both followed a close-to-isometric growth pattern. Immature S. canicula possessed a larger mesencephalon and diencephalon, highlighting the importance of vision in this life period, while mature specimens had enlarged olfactory bulbs, indicating that olfaction may be more important after the animal attains sexual maturity. In respect of sexual dimorphism, males had a larger cerebellum and medulla oblongata, while females had enlarged telencephalon and olfactory bulbs.