The surface of multi-wall carbon nanotubes (MWNTs) was functionalized by covalent linking of long alkyl chains. Such functionalization led to a much better tube dispersion in organic solvents than pristine nanotubes, favored the formation of homogenous nanocomposite films, and yielded good interfacial bonding between the nanotubes and two polymer matrices: a thermoset (Epon 828/T-403) and a thermoplastic (PMMA). Tensile tests indicated, however, that the reinforcement was greatly affected by the type of polymer matrix used. Relative to pure PMMA, a 32% improvement in tensile modulus and a 28% increase in tensile strength were observed in PMMA-based nanocomposites using 1.0 wt% nanotube filler. Contrasting with this, no improvement in mechanical properties was observed in epoxy-based nanocomposites. The poorer mechanical performance of the latter system can be explained by a decrease of the crosslinking density of the epoxy matrix in the nanocomposites, relative to pure epoxy. Indeed we demonstrate that the presence of nanotubes promotes an increase in the activation energy of the curing reaction in epoxy, and a decrease of the degree of curing.