We demonstrate the success in self-assembling pyrene-modified Dawson–Wells-type polyoxometalates (POMs) with single walled carbon nanotubes (SWCNTs) by means of π–π interactions. In this context, the immobilization of POMs onto SWCNTs is corroborated by aberration-corrected high-resolution electron microscopy, thermogravimetric analysis, and Raman spectroscopy. From steady-state and time-resolved photophysical techniques we derived evidence for mutual interactions between SWCNTs and POMs in the excited states. The latter are the inception to a charge transfer from the SWCNTs to the POMs. Our results corroborate the suitability of POM–SWCNTs assemblies for photoactive molecular devices.