Abstract: In order to improve the flame retardant properties of ramie fabrics used as the reinforcing material in composites, amino-functionalized multiwall carbon nanotube (MWCNT)-ammonium polyphosphate (APP) and polyethylenimine (PEI)-APP intumescent flame retardant multilayer coatings were constructed on the surfaces of ramie fabric via layer-by-layer assembly method firstly. Then, the modified ramie fabrics were composed with benzoxazine resin to prepare ramie fabric/benzoxazine resin laminates, and the thermal degradation behaviour, flame retardant properties and mechanical properties of laminates were investigated. The results show that compared to the pristine ramie fabric/benzoxazine resin laminate, the peak values of heat release for the laminates containing MWCNT-APP and PEI-APP intumescent flame retardant multilayer coatings decrease from 106.6 W·g^-1 to 53.4 W·g^-1 and 53.0 W·g^-1, the total heat release decrease from 12.3 kJ·g^-1 to 7.6 kJ·g^-1 and 9.0 kJ·g^-1, the limiting oxygen indexes increase from 23.5 to 27.2 and 27.0, the UL94 level increase from no rating to V-0 and V-1 levels, the flexural strengths increase from 81 MPa to 122 MPa and 143 MPa, the flexural elongations at break increase from 1.2% to 1.4% and 1.7%, and the tensile properties also show improvements to a certain degree. The conclusions obtained show that using MWCNT-APP and PEI-APP intumescent flame retardant multilayer coatings can not only improve the flame retardant properties of laminates, but also improve the mechanical properties at the same time.