Imidazolium ionic liquids (IL) are salts with ionic-covalent crystalline structures presenting melting temperatures up to 100 °C. Due to the unusual imidazolium derived IL’s characteristics, e.g. structural organization and high thermal and chemical stability, these have shown great potential as templates for materials synthesis and processing [1,2]. The imidazolium IL exist as self-assembled polymeric supramolecular structures, driven main by hydrogen bonds and π-π stacking. These highly interactive characteristics allow their use for organizing the system to which they are applied. The sol-gel process is another powerful source for the preparation of surface and interface controlled materials, allowing tuning of the physicochemical properties from the first stages of preparation [3,4]. This study describes the application of IL, as well as their in situ formed sol-gel silica hybrids, into the isotactic polypropylene (iPP) melt-processing. This allowed the preparation of ordered iPP and polypropylene-silica nanocomposites. The processed iPP materials were characterized by TGA, DSC, XRD, TEM and DMA. The silica-IL hybrids application showed improved filler dispersion in the polymer matrix, indicating that IL can act as a coupling agent. Melt blending of iPP with either IL or silica-IL hybrid promoted increase in the crystallization temperature, which indicated a nucleation effect. Also, the resistance to thermal decomposition was increased. Especially applying the silica-IL hybrid, the XRD and DSC profiles showed that IL with long aliphatic cation side-chains promoted β-nucleation of iPP. The application of neat IL in the melt processing causes the disruption of their ordered structures, justifying the stronger nucleating effect when IL is confined into the silica pores.