A two‐component hydrogelator (16‐A)2‐V2+, comprising an l‐alanine‐based amphiphile (16‐A) and a redox‐active viologen based partner (V2+), is reported. The formation the hydrogel depended, not only on the acid‐to‐amine stoichiometric ratio, but on the choice of the l‐amino acid group and also on the hydrocarbon chain length of the amphiphilic component. The redox responsive property and the electrochemical behavior of this two‐component system were further examined by step‐wise chemical and electrochemical reduction of the viologen nucleus (V2+/V+ and V+/V0). The half‐wave reduction potentials (E1/2) associated with the viologen ring shifted to more negative values with increasing amine component. This indicates that higher extent of salt formation hinders reduction of the viologen moiety. Interestingly, the incorporation of single‐walled carbon nanotubes in the electrochemically irreversible hydrogel (16‐A)2‐V2+ transformed it into a quasi‐reversible electrochemical system.