In this work, a study for understanding the role played by [ClBmim], [BF4Bmim], [PF6Bmim], and [CH3SO3Bmim] ionic liquids (ILs) in the synthesis of zeolites is presented. The use of [ClBmim] and [CH3SO3Bmim] ILs, as reported earlier [ Chem. Eur. J. 2013 , 19 , 2122 ] led to the formation of MFI or BEA type zeolites. Contrary, [BF4Bmim] and [PF6Bmim] ILs did not succeed in organizing the Si-Al network into a zeolite structure. To try to explain these results, a series of quantum mechanical calculations considering monomers ([XBmim]) and dimers ([XBmim]2) by themselves and plus cosolvent (water or ethanol) were carried out, where X ≡ Cl(-), BF4(-), PF6(-), or CH3SO3(-). Our attention was focused on the similarities and differences among the two types of cosolvents and the relation between the structure and the multiple factors defining the interactions among the ILs and the cosolvent. Although a specific pattern based on local structures explaining the different behavior of these ILs as a zeolite structuring template was not found, the calculated interaction energies involving the Cl(-) and CH3SO3(-) anions were very close and larger than those for BF4(-) and PF6(-) species. These differences in energy can be used as an argument to describe their different behavior as structure directing agents. Moreover, the topology of the cosolvent is also an ingredient to take into account for a proper understanding of the results.