Double-walled carbon nanotube (DWNT)-CdSe heterostructures with the individual nanoscale building blocks linked together by 4-aminothiophenol (4-ATP) have been successfully synthesized using two different and complementary routes, i.e. covalent attachment and non-covalent π-π stacking. Specifically, using a number of characterization methods, we have probed the effects of these differential synthetic coupling approaches on the resulting CdSe quantum dot (QD) coverage on the underlying nanotube template as well as the degree of charge transfer between the CdSe QDs and the DWNTs. In general, based on microscopy and spectroscopy data collectively, we noted that heterostructures generated by non-covalent π-π stacking interactions evinced not only higher QD coverage density but also possibly more efficient charge transfer behavior as compared with their counterparts produced using covalent linker-mediated protocols.