Density functional theoretical calculations predicted non‐coplanar twisted geometry for two new imidazo[1,2‐a]pyridine derivatives, Imp and ImBt. Analysis of single‐crystal of Imp asserted the non‐coplanar twisted geometry, which is implicated in aggregation induced emission (AIE) of small aromatic molecules. Universal quenching by water was observed in aqueous THF solutions of Imp and ImBt, but they showed AIE effect when the water content was more than 80 %. Non‐fluorescent solutions of Imp and ImBt in THF‐water (7 : 3 v/v) mixture turned fluorescent on addition of specific metal ions prompting their potential to be explored for turn‐on sensor applications. While ImBt showed AIE response to Cd2+, Hg2+ and Al3+, Imp displayed AIE effect only to Cd2+ ions, under identical conditions. Absence of interference from common metal ions (including Hg2+ and Al3+) led to selective formation of Imp‐CdCl2 (1 : 1) complex, which offered the limit of detection of Cd2+ to be 19.2 μM. The observed selectivity for Cd2+ permitted the use of Imp in the imaging of live Rhizoctonia oryze contaminated with Cd2+ ions.