A new solvent stimuli-responsive metallogel (VGel) was synthesized through the introduction of vanadium ions into an adenine (Ade) and 1,3,5-benzene tricarboxylic acid (BTC) organogel, and its supramolecular self-assembly was investigated from a computational viewpoint. A relationship between the synthesized VGel integrity and the self-assembly of its components is demonstrated by a broad range of molecular dynamics (MD) simulations, an aspect that has not yet been explored for such a complex metallogel in particular. MD simulations and Voronoi tessellation assessments, both in agreement with experimental data, confirm the gel formation. Based on excellent water stability and the ethanol/methanol stimuli-responsive feature of the VGel an easy-to-use visualization assay for the detection of counterfeit liquor with a 6% (v/v) methanol limit of detection in 40% (v/v) ethanol is reported. These observations provide a cheap and technically simple method and are a step towards the immersible screening of similar molecules in methanol-spiked beverages.