Zeolites and mesoporous silicas are porous materials with important applications in catalysis, gas storage, and separation. Zeolite crystals form in the presence of cationic surfactants that act as structure directing agents (SDAs). The way SDAs control the nucleation and polymorphs selection in zeolites is not fully understood. The formation of mesoporous silica is templated by liquid crystalline mesophases that result from frustrated attraction between silicates and long-chain SDAs. Experiments indicate that surfactants C n H 2n+1 (CH 3 ) 3 N + with n > 6 yield mesoporous silicas, and the one with n = 6 produces a zeolite. This suggests that the driving force toward mesophase formation is also present for small organocations, but is overcome by the ability of silica to wrap a crystal lattice around them. Here we use molecular dynamics simulations to investigate whether the existence of metastable mesophases can play a role in the nucleation and polymorph selection of zeolitic crystals. As a proof of concept, we investigate the phase behavior of simple mesogenic mixtures of SDAs and a network former T that favors tetracoordinated crystals. We represent the network-former T by Stillinger−Weber models of water and silicon, in lieu of silica, because a computationally efficient silica potential that would allow for the spontaneous nucleation of zeolites in molecular dynamics simulations is not yet available. The mixtures of T and SDA produce a rich phase diagram that encompasses the sII clathrate and at least six zeolites, including sigma-2 (SGT). We find that the nucleation of SGT is not assisted by a mesophase. The nucleation of the other five zeolites of this study, however, is facilitated by the existence of metastable mesophases that decrease the nucleation barriers and direct the selection of the crystal polymorph. Together with the experimental support for mesophases in mixtures of silicates and SDAs, our results for model systems suggest that metastable mesophases could play a prominent role in promoting the nucleation and polymorph selection of some zeolites.