Nowadays, nanotechnology represents a well-established approach, suitable for designing, producing, and applying materials to a broad range of advanced sectors. In this context, the use of well-suited “nano” approaches accounted for a big step forward in conferring optimized flame-retardant features to such a cellulosic textile material as cotton, considering its high ease of flammability, yearly production, and extended use. Being a surface-localized phenomenon, the flammability of cotton can be quite simply and effectively controlled by tailoring its surface through the deposition of nano-objects, capable of slowing down the heat and mass transfer from and to the textile surroundings, which accounts for flame fueling and possibly interacting with the propagating radicals in the gas phase. In this context, the layer-by-layer (LbL) approach has definitively demonstrated its reliability and effectiveness in providing cotton with enhanced flame-retardant features, through the formation of fully inorganic or hybrid organic/inorganic nanostructured assemblies on the fabric surface. Therefore, the present work aims to summarize the current state of the art related to the use of nanostructured LbL architectures for cotton flame retardancy, offering an overview of the latest research outcomes that often highlight the multifunctional character of the deposited assemblies and discussing the current limitations and some perspectives.