Methods to in-situ construct nanostructures are the key tools of nanotechnology. Herein, for the enforced combination of two nanomaterials, an in-situ combination technique, 'electrohydrodynamic jetting of countercharged nozzles (EJC)', was explored. EJC used an attraction force between negative and positive surface charges generated by electrohydrodynamic spinning and spraying. The obtained nanostructures were dependent on the types of materials and jetting conditions. Poly(methyl methacrylate) nano- or micro-fibers were uniformly combined with polystyrene nano- or microparticles. When lipoic acid (an antioxidant drug) was used instead of polystyrene, composite structures of fibers and surface nanodots resulted. The method could also enforce gold nanoparticles stick onto the surface of fibers. EJC is an efficient technique to fabricate composite nanostructures using materials with a wide range of properties.