In the shipbuilding sector (cruises, ferries, etc.), the design and control constraints applied to improve the fire safety conditions of naval vessels are acquiring important relevance. Research activities have aimed at enhancing the fire resistance of structures and surface coatings to make ships’ working environments safer, trying to combine performance, durability and low costs. In this context, the aim of this paper is to develop and optimize flame-retardant coatings for naval applications. In particular, in an acrylic carrier, Mg(OH)2 and Al(OH)3 fillers were added to exalt the fire resistance capabilities of the coatings. Furthermore, the effect of the particle size of the hydroxides on the coatings’ fire resistance was investigated. The coatings were studied by structural (XRD), thermo-physical (TG) and morphological (SEM) characterization to evaluate their thermal stability and the damage level due to fire exposition. Specifically, fire reaction tests were applied at different fire exposure times (15 s, 30 s) to estimate the fire resistance of the proposed coatings compared to the commercial reference. The results show that the coatings based on aluminum and magnesium hydroxides exhibit favorable fire resistance. Particularly, effective performances were observed for short times of exposure to direct flames. Furthermore, the temperature monitoring of the steel alloy support during the test allowed us to evaluate the degree of insulation of the coating, highlighting a better result for the specimen filled with Mg(OH)2, making this product promising for its optimization in this context.