Blends of polypropylene (PP) and natural rubber (NR) with different loadings (1, 3, 5, and 7 wt%) of multiwalled carbon nanotubes (MWCNTs) are prepared by melt blending process. Influence of MWCNT concentration and blend ratio on the surface energy characteristics and wetting behavior of PP/NR/MWCNT nanocomposites are investigated using contact angle measurements with water and dimethyl sulfoxide. The surface energy, work of adhesion, spreading coefficient, interfacial energy, and interaction parameter are measured for all composites. It is understood that contact angle value of nanocomposites increases with the increasing MWCNT content and is attributed to the increase in hydrophobic nature of blends due to the presence of hydrophobic MWCNTs. Similar trend of variation of contact angle is found for nanocomposites with different blend ratio. The study also reveals that contact angle and wetting property of the nanocomposite increases with increase in the surface roughness of the sample. Results of contact angle studies show good agreement with the morphology of nanocomposites obtained by atomic force microscopy techniques.