Three groups of pyrrolidinium headgroup-based gemini surfactants of 1,1'-(propane-1,3-diyl) bis(1-alkyl pyrrolidinium) bromide, in categories of symmetric CmC3CmPB (m = 10, 12, 14), dissymmetric CmC3C14PB (m = 10, 12, 14) and CmC3CnPB (m = 8, 10, 12, m + n = 24) surfactants, are studied using equilibrium surface tension, conductivity, fluorescence, and NMR techniques. The importance of the dissymmetry on the micellization has been revealed in detail. The increase in the hydrophobic chain length m for CmC3CmPB and CmC3C14PB or in the dissymmetry (n/m) for CmC3CnPB can strengthen the aggregation...