The formation and annealing of various kinds of defects in the framework of highly siliceous MFI-type zeolites, as evidenced by high-resolution solid-state 29Si n.m.r., can be explained by considering the systematic influence of synthesis parameters and postsynthesis treatments. High pH values and high concentrations of alkali metal and fluoride ions prevent a complete polycondensation of the silicate species and generate materials that contain significant levels of nonbonding point defects. By contrast, a high crystallization temperature results in the ready hydrolysis of the terminal Si-O − groups, leading to structures containing fewer defects. A large number of T vacancies (hydroxyl nests) are created in zeolites crystallized at low temperatures in the presence of high Pr 4N + concentations and in the absence of F − or Na + ions. Such conditions favor the formation of double-5-ring silicate anions. The hypothesis, that such species may further condense, conducting to frameworks with an important number of empty T-sites, is proposed. On the basis of these findings, ideal synthesis conditions can be proposed to produce (Si) MFI zeolites that contain a minimum number of defects. Various postsynthesis treatments, namely, different calcination conditions followed, or preceded, by selected ionic (akali cation) exchanges, result in a partial or a nearly total healing of these defects in the final materials.