In this review, we recollect and discuss the most relevant advancement in crystallographic aspects of alkali nitrates compounds published since 1975, the year of publication of the last review by Rao et al. about some topics discussed here. This review is focused in five nitrate compounds of the first periodic table column: LiNO3, NaNO3, KNO3, RbNO3 and CsNO3. For each one, we have compiled the information about crystal structure, polymorphism and phase transition, crystal growth and crystal morphology, and the phase diagram and solid-state miscibility results. Considerable numbers of papers have been published in the last 40 years, in particular in relation to binary phase diagrams and solid-state miscibility of alkali nitrates. A variety of phase diagram descriptions appears in the 10 possible binary combinations for the five compounds. To finish, we discuss and propose a geometric model in order to explain the different binary phase diagrams observed between these compounds.