We examined the optoelectronic properties of atomically thin 1D van der Waals heterostructures comprising the single-walled carbon nanotubes (NT) wrapped by insulating BN NT layers and MoS2 NT outer layers (C@BN@MoS2NT). We will present the equilibrium properties of such materials (through optical absorption, transmission, reflection, ellipsometry, Raman scattering, THz spectroscopy, and XPS studies) along with the transmission electron microscopy measurements. Through all of these techniques, we evaluated intertube excitonic interactions in addition to the charge transport characteristics of a large area 1D heterostructure. In addition, non-equilibrium, ultrafast pump–probe spectroscopy across the visible and terahertz frequency ranges identified that, in the MoS2 nanotubes, excitons coexisted with a prominent population of free charges.