In this study, poly (vinyl alcohol) (PVA) composites reinforced by multiwall carbon nanotubes (MWCNTs) functionalized with either phenolic hydroxyl groups (MWCNTs-f-OH) or PVP molecule (PVP@MWCNTs) were fabricated. The objective was to elucidate the effect of different MWCNTs surface functionalization on the mechanical properties of the nanocomposites. It was found that both of PVP@MWCNTs and MWCNTs-f-OH had a good dispersion in PVA matrix. However, the MWCNTs-f-OH had stronger effective interfacial interaction with PVA matrix than PVP@MWCNTs, owe to the formation of hydrogen bonds between MWCNTs-f-OH and PVA. The stress-strain measurements showed that the Young's modulus and tensile strength of MWCNTs-f-OH/PVA with only 1.0 wt.% contents increased by 200 and 100% compare with that of PVA, respectively. The findings of this experimental study emphasized the critical role of MWCNTs surface morphology in determining the mechanical properties of nanocomposites, and shed new light on understanding and advancing the properties of carbon nanotube based composites.