New cholesterol-based gelators bearing a 4-, 3-, or 2-pyridyl group (1, 2, or 3, respectively) have been designed. Compound I gelled 16 of the 19 solvents tested, indicating that I acts as a very versatile gelator. The gelation ability of compound 2 was significantly improved by added AgOTf, owing to an Ag(I)-pyridine interaction. The findings indicate that the pyridyl group is very useful to impart new functions to organogel systems.