Bast fibers are one of most widely used types of cellulosic natural fibers. Flax fibers, a specific type of bast fiber, have historically been used as reinforcements in composites because they offer competitive advantages, including environmental and economic benefits, over mineral-based reinforcing materials. However, the poor interfacial properties due to the hydrophilicity of flax fibers and the hydrophobicity of most polymer matrices reduce the mechanical performance of flax thermoset composites. On the other hand, the structure of flax fiber is more complex than synthetic fibers, which causes most of traditional mechanical tests from the transverse direction to evaluate the interfacial properties of flax composites are not valid. In this study, the physical and chemical properties of flax fibers, vinyl ester resin and their composites are investigated. A comprehensive understanding of flax fiber, vinyl ester systems and their composites has been established. Surface modifications to the flax fiber and chemical manipulations on vinyl ester systems have been studied to improve the interfacial properties of flax/vinyl ester biocomposites. A new chemical manipulation method for vinyl ester system has been invented. The specific interlaminar shear strength of alkaline treated flax/VE with 1.5% AR shows approximately 149% increase than untreated flax/VE composites. NaOH/Ethanol treated flax/VE with AR shows 33% higher in specific flexural modulus and 73% better in specific flexural strength than untreated flax/VE composites. In addition, AR modified alkaline treated flax composites performs approximately 75% better in specific tensile modulus and 201% higher in specific tensile strength than untreated flax/VE composites. Flax/VE composite with high elastic modulus, which is higher than their theoretically predicted elastic modulus, was achieved. The effects of thermal properties of flax fibers and vinyl ester resin systems on the interfacial properties of their biocomposites were also studied. The theory of modifying the thermal properties of flax and vinyl ester to improve the interfacial adhesion has been proved by the study of the thermal residual stresses in their composites by XRD techniques.