The experimental conditions necessary for stabilising irbesartan (IBS) tautomers in solution and selectively obtaining the desmotropic crystal forms are presented herein. 1H and 2H tautomers were stabilized in specific solution conditions and the 2H-tetrazole⋯imidazole interaction was confirmed by solution-state NMR. The results showed that highly polar and polarisable solvents (higher values of the electrostatic factor (EF)) lead to the crystallisation of IBS form B. Furthermore, the variations of pH in methanol, in turn, determined the crystallisation of desmotropes A and/or B.