Endohedral metallofullerenes (EMFs) have become an important class of molecular materials for optoelectronic applications. The performance of EMFs is known to be dependent on their symmetries and characters of the substituents, but the underlying electron dynamics remain unclear. Here we report a systematic study on several scandium EMFs and representative derivatives to examine the cage symmetry and substituent effects on their photoexcited electron dynamics using ultrafast transient absorption spectroscopy. Our attention is focused on the visible-light (530 nm as a demonstration) photoexcited electron dynamics, which is of broad interest to visible-light solar energy harvesting but is considered to be quite complicated as the visible-light photons would promote the system to a high-lying energy region where dense manifolds of electronic states locate. Our ultrafast spectroscopy study enables a full mapping of the photoinduced deactivation channels involved and reveals that the long-lived triplet exciton plays a decisive role in controlling the photoexcited electron dynamics under certain conditions. More importantly, it is found that the opening of the triplet channels is highly correlated to the fullerene cage symmetry as well as the electronic character of the substituents.