A panel of dicationic ionic liquids (DILs) with different rigid xylyl (ortho, meta, para) spacers and different anions (bromide and tungstate) has been synthetised and characterised through different experimental and computational techniques. Differences and analogies between the systems are analysed using information derived from their DFT structures, semiempirical dynamics, thermal behaviour, and catalytic properties versus the well-known reaction of CO₂ added to epichlorohydrin. A comparison between the proposed systems and some analogues that present non-rigid spacers shows the key effect displayed by structure rigidity on their characteristics. The results show an interesting correlation between structure, flexibility, properties, and catalytic activity.