Nepheline (Na6K2Al8Si8O32) is a rock-forming tectosilicate mineral which is by far the most abundant of the feldspathoids. The crystallization in nepheline-based glass-ceramics proceeds through several polymorphic transformations mainly orthorhombic, hexagonal, cubic depending on their thermochemistry. However, the fundamental science governing these transformations is poorly understood. In this article, an attempt has been made to elucidate the structural drivers controlling these polymorphic transformations in nepheline-based glass-ceramics. Accordingly, two different sets of glasses (meta-aluminous and per-alkaline) have been designed in the system Na2O-CaO-Al2O3-SiO2 in the crystallization field of nepheline and synthesized by the melt-quench technique. The detailed structural analysis of glasses has been performed by Si-29, Al-27, and Na-23 magic-angle spinning nuclear magnetic resonance (MAS NMR), and multiple-quantum MAS NMR spectroscopy, while the crystalline phase transformations in these glasses have been studied under isothermal and non-isothermal conditions using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and MQMAS NMR. Results indicate that the sequence of polymorphic phase transformations in these glass-ceramics is dictated by the compositional chemistry of the parent glasses and the local environments of different species in the glass structure; for example, the sodium environment in glasses became highly ordered with decreasing Na2O/CaO ratio, thus favoring the formation of hexagonal nepheline, while the cubic polymorph was the stable phase in SiO2-poor glass-ceramics with (Na2O+CaO)/Al2O3 > 1. The structural origins of these crystalline phase transformations have been discussed in the paper.