5,17-Difunctionalized calix[4]arenes 1a,b were found to function as low molecular-weight organic gelators. They formed organogels with a variety of organic solvents. SEM images showed 1a formed stacked structures in the xerogels. Single-crystal X-ray analysis of 1c as well as AFM, XRD, and SAXS measurements of 1a indicated that the xerogels contained lamellar structures of the calix[4]arenes.