Abstract Naturally occurring van der Waals crystals have brought unprecedented interest to nanomaterial researchers in recent years. So far, more than 1800 layered materials (LMs) have been identified but only a few insulating and naturally occurring LMs were deeply investigated. Phyllosilicate minerals, which are a class of natural and abundant LMs, have been recently considered as a low-cost source of insulating nanomaterials. Within this family an almost barely explored material emerges: phlogopite (KMg₃(AlSi₃)O₁₀(OH)₂). Here we carry out a high throughput characterization of this LM by employing several experimental techniques, corroborating the major findings with first-principles calculations. We show that monolayers (1L) and few-layers of this material are air and temperature stable, as well as easily obtained by the standard mechanical exfoliation technique, have an atomically flat surface, and lower bandgap than its bulk counterpart, an unusual trend in LMs. We also systematically study the basic properties of ultrathin phlogopite and demonstrate that natural phlogopite presents iron impurities in its crystal lattice, which decreases its bandgap from about 7 eV to 3.6 eV. Finally, we combine phlogopite crystals with 1L-WS₂ in ultrathin van der Waals heterostructures and present a photoluminescence study, revealing a significant enhancement on the 1L-WS₂ optical quality (i.e. higher recombination efficiency through neutral excitons) similarly to that obtained on 1L-WS₂/hexagonal boron nitride heterostructures. Our proof-of-concept study shows that phlogopite should be regarded as a good and promising candidate for LM-based applications as a low-cost layered nanomaterial.