Highly luminescent, core–shell, single-walled carbon nanotube–poly[2-methoxy-5-(2′-ethylhexyloxy)−1,4-phenylene vinylene] (MEH-PPV) one-dimensional networks were synthesized by a multicycle unstable micellization method. The current–voltage data indicated that the charge transport within the nanowire network remained Ohmic, with the differential conductance scaling linearly with temperature in the temperature range of about 120 to 300 K. Further analysis based on the comparative study involving photoluminescence and Raman spectroscopic tests pointed to interchain interactions and nanotube–polymer interface as primary factors influencing the electronic characteristics of the processed samples. Likewise, steady-state photoconduction tests confirmed that the heterointerface played a dominant role behind the increased photoresponse induced by exciton annihilation at a low bias regime. The study helped us identify the underlying physical mechanisms that controlled the optical, electrical, and photoconduction properties of the MEH-PPV–carbon nanotube heteronetworks. Potentially, this will open a door to the development of next generation, low-cost, all-organic nanooptoelectronic devices and systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40029.