Much attention has been paid to diosgenin saponins because of their various bioactivities, whereas their gelation ability has never been reported. We synthesized some new saponins with pentose directly connected to diosgenin in a shorter procedure, which neither removed the acetyl group of the anomeric hydroxyl group selectively nor activated it and led to a higher yield, compared with the common synthesis of other diosgenyl saponins. We found these compounds are gelators of various organic solvents and their gel formation was studied with FTIR and SEM. This serendipitous discovery enriches the diversity of steroidal small molecular gelators. Meanwhile, single crystal X-ray analysis gave additional information about their intermolecular interactions in the solid state.