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The properties of polymeric nanofibers can be tailored and enhanced by properly managing the structure of the polymer molecules at the nanoscale. Although electrospun polymer fibers are increasingly exploited in many technological applications, their internal nanostructure, determining their improved physical properties, is still poorly investigated and understood. Here, we unravel the internal structure of electrospun functional nanofibers made by prototype conjugated polymers. The unique features of near-field optical measurements are exploited to investigate the nanoscale spatial variation of the polymer density, evidencing the presence of a dense internal core embedded in a less dense polymeric shell. Interestingly, nanoscale mapping the fiber Young’s modulus demonstrates that the dense core is stiffer than the polymeric, less dense shell. These findings are rationalized by developing a theoretical model …