Herein we report on the facile and large‐scale syntheses and characterizations of a series of transition metal‐containing ionic liquids (MILs), namely [C12MMIm]n[MCl4] (M=Fe3+, n=1; M=Cu2+, Co2+, Zn2+, Cd2+, n=2; C12MMIm=1‐decyl‐2,3‐dimethylimidazolium) by simply stoichiometrically mixing metal chlorides and the IL [C12MMIm]Cl. All of the compounds could be obtained in crystalline state at room temperature in nearly 100% yield. Single‐crystal X‐ray diffraction analysis reveals that all the MIL crystals belong to the space group of P21/c, consisting of [C12MMIm]+ cations and halometallate anions that interact with each other giving rise to supramolecular layered structures via C−H⋅⋅⋅Cl hydrogen bonding and anion‐π interactions. Thermal properties of the five compounds were studied by differential scanning calorimetry (DSC) and thermogravimetry (TG), revealing reversible phase transitions near room temperature. Interestingly, these MILs are air‐ and moisture‐stable when stored in ambient conditions. The [C12MMIm]n[MCl4] (M=Cu2+, Co2+ and Fe3+ ) crystals exhibited obvious colour‐change when exposed to ammonia (NH3) gas, indicating potential applications in ammonia detection.