The excellent comprehensive properties of microfiber synthetic leathers have led to their wide application in various aspects of our lives. However, the issue of flammability remains a significant challenge that needs to be addressed. Nowadays, the bio-based chemicals used in the flame-retardant materials have extremely grabbed our eyes. Herein, we developed an ecologically friendly flame-retardant microfiber synthetic leather using phosphorus-free layer-by-layer assembly technology (LBL) based on natural polysaccharide alginate (SA) coupled with polyethyleneimine (PEI) and 3-aminopropyltriethoxysilane (APTES). The effect of different LBL coating systems on the flame retardancy of microfiber synthetic leather was investigated. The results demonstrated that the introduction of APTES can completely inhibit the melt-dripping by enhancing char formation through silica elements. Furthermore, the trinary coating system consisting of SA/APTES/PEI exhibited excellent flame retardancy by combining gas-phase action from PEI and condensed-phase function from APTES. This modified microfiber synthetic leather showed a significantly higher limiting oxygen index (LOI) value of 33.0 % with no molten droplet. Additionally, the SA-based coating slightly suppressed the heat release, resulting in a 20 % reduction in total heat release during the combustion test. Overall, this work presents a facile and environmentally-friendly approach for achieving flame-retardant and anti-dripping microfiber synthetic leather.