Wildfires are becoming more intense and more frequent, ravaging the habitations and ecosystems in their path. One solution to reducing the risk of damage to buildings and other structures during a fire event is the use of fire-retardant coatings that can stop or slow down the spread of flames, especially for textile materials. The present study focuses on the preparation and application of halogen-free boron/bentonite-based polymeric fire-retardant (FR) hybrid coating formulations for fabrics such as cotton (CO) and polyester (PE) fibers. For the preparation of FR composites, two types of boron derivatives, disodium octaborate and zinc borate, were used in combination with sodium bentonite. A styrene-acrylic copolymer was specifically synthesized and used as a coating binder for FR components to apply on fabrics. The properties of the synthesized copolymer and FR composites were characterized with a particle size analysis, FTIR spectroscopy, a dynamic mechanical thermal analysis (DMTA), and rheological measurements. The obtained hybrid composites based on styrene-acrylic copolymers and two different inorganic fillers were applied on cotton (CO) and polyester (PE) fabrics with a screen-printing technique, and the flame retardancy performance of the finished textile samples was investigated by means of flame spread and limit oxygen index (LOI) tests. The findings showed that the FR-composite-coated fabrics had higher LOI values and much decreased flame spread rates in comparison with uncoated ones. Among the boron derivatives, the composites prepared with disodium octaborate (FR-A) had much more pronounced LOI values and decreased flame spread behavior in comparison with the composite with zinc borate (FR-B). When compared to a commercial product, the FR-A composite, in conjunction with the specially synthesized polymer, demonstrated commendable fire retardancy performance and emerged as a promising candidate for a halogen-free waterborne fire-retardant coating for fabrics.