The search for low molecular weight hydrogelators (LMWH) with varying structural motif is getting intense because of its potential application in the field of biomedicines as well as the diversified area of nano-biotechnology. In this paper, we have developed hydrogels of simple cationic dipeptide amphiphiles (1-6) that have a wide range of minimum gelation concentration (MGC), 12-0.25% (w/v) in plain water. The self-aggregation behavior of these thermoreversible hydrogelators has been investigated through different spectroscopic and microscopic techniques. A balanced participation of hydrophilicity and hydrophobicity is the major driving force for gelation, which could be modulated by a minute change in the architecture of the amphiphile head. The prospective use of this material in controlled release suggests that this system could also be applied as the drug delivery vehicle. Moreover, the presence of a biodegradable amide linkage susceptible to base or enzyme-catalyzed hydrolysis increases its probable applications as biomaterials.