A pyridyl azo‐based progelator 1 has been designed and synthesized for selective detection of Hg2+ and Ag+ ions in sol‐gel media. Compound 1 acts as nongelator in DMSO‐H2O (1:1, v/v) while its aldehyde‐counterpart 3 forms stable gel under identical conditions. The specific Hg2+‐induced deprotection of the thioacetal functionality in 1 results in in‐situ formation of the precursor aldehyde 3 and thereby induces sol‐to‐gel transformation in DMSO‐H2O (1:1, v/v). Gelation is also observed in the presence of Ag+ ion. Interestingly, the gelation modes of 1 in the presence of Hg2+ and Ag+ ions are different. The Hg2+‐induced gelation involves dosimetric sensing while the Ag+‐induced gelation involves simple metal‐ligand non‐covalent interaction, as established by using different chelating agents and spectroscopic techniques. The design of metal‐responsive low molecular weight gelators (LMWGs) involving protection/deprotection of functional groups in gelator structure is rarely investigated in the literature and hence draws attention.