The electronic structure of semiconducting carbon nanotubes selected through polymer functionalization is routinely verified by measuring the spectral van Hove singularity signature under ultraclean vacuum conditions. Interpreting the effect of unperturbed polymer adsorption on the nanotube energetic bands in solvent media is experimentally challenging owing to solvent molecular crowding around the hybrid complex. Here, a liquid-based scanning tunneling microscope and spectroscope operating in a noise-free laboratory is used to resolve the polymer-semiconducting carbon-nanotube-underlying graphene heterostructure in the presence of encompassing solvent molecules. The spectroscopic measurements highlight the role of polymer packing and graphene landscape on the electronic shifts induced in the nanotube energy bands. Together with molecular dynamics simulations, our experimental findings emphasize the necessity of recording physicochemical and electronic properties of liquid-phase solubilized hybrid materials in their native state.