Continuous core-shell nanofibers with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block co-polymer/polymer derived ceramic (PDC) precursor nanocomposites as cores enveloped in rigid polyacrylonitrile (PAN) shells were nanomanufactured using coaxial electrospinning. The cylindrical confinement imposed by the rigid shell led to ordered morphologies in the core not observed in bulk block copolymer nanocomposites.