This work studies the binaries of 1-butyl-X-methylpyridinium tetrafluoroborate [bXmpy][BF4] (X = 2, 3, and 4) with four 1,?-dichloroalkanes, omega = 1-4, using the results obtained for the mixing properties h(E) and v(E) at two temperatures. The three isomers of the ionic liquid (IL) are weakly miscible with the 1,omega-dichloroalkanes when omega >= 5 and moderately soluble for omega= 4. The vEs of all the binaries present contractive effects, v(E) < 0, which are more pronounced with increasing temperature; the variation in v(E) with omega is positive, although this changes after ? = 4 due to problems of immiscibility. The energetic effects of the mixing process are exothermic in the solutions with the shorter dichloroalkanes, omega = 1 and 2, and this effect increases slightly with temperature. However, mildly exothermic effects are found in the binaries with larger halides, where (dh(E)/dT) > 0. The experimental data are correlated with a suitable equation. The study is completed with 1H NMR measurements of both the pure compounds and some of the solutions, which showed minor diamagnetic shifts with increasing IL compositions, related to the anisotropy of the pyridine ring. The variation in h(E) with omega for a same IL, due to an increase in the contact surfaces, is related to the reduction in polarity which, in turn, depends on the smaller chemical shifts of the pure dihalide compounds. The COSMO-RS method determines the energetic effects of the mixing process and predicts an exothermic contribution for the electrostatic Misfit-interaction which is quantitatively very similar for the three IL isomers. The differences proposed by the model are mainly reflected in the van der Waals interactions, which are exothermic and clearly influenced by the position of the methylene group in the IL. The contribution made by hydrogen bonds is negligible.