Tensile and microstructural properties of multiwall carbon nanotube (MWCNT)/polyisoprene (PI) composites have been investigated after cross-linking achieved purely by simultaneous high-pressure high-temperature treatment. The method enables gradual increase of the cross-link density without interference of vulcanization chemicals, and the results suggest a link between an interfacial PI layer wrapped/coated on the MWCNTs and reinforcement in carbon nanotube (CNT)/PI composites. The interfacial layer, which is augmented by high-pressure treatment, was detected indirectly in swelling experiments and also reflected in results of atomic force microscopy. The results imply more efficient load transfer and mechanical reinforcement by CNTs with improved interfacial layer and that changes in the layer can be probed by swelling measurements.