Multi-walled carbon nanotubes synthesized from ethanol flames (F-MWCNTs) and nanotubes functionalized by n-hexadecylamine (H-MWCNTs) were applied to the preparation of glass fiber/vinyl ester composites by overcoating the original glass fiber. Scanning electron microscopy of the composites containing multi-walled carbon nanotubes (MWCNTs) showed better bonding between the glass fiber and the resin matrix which may be attributed to the existence of a flexible interphase introduced by the nanotubes. It was found that the bonding in the composites treated with H-MWCNTs was much stronger. Moreover, the dynamic mechanical properties and impact strengths of the resulting composites were investigated. The results revealed that treating glass fiber with MWCNTs effectively improved the mechanical properties of the composite materials. Furthermore, the dynamic properties showed that H-MWCNTs have become integral parts of the crosslinked polymer structure, rather than acting as separate fillers.