Plasmonic enhancement for electron–hole separation efficiency and visible light photocatalysis was achieved by Pd nanocube decoration on a ZnO nanolayer coated onto electrospun polymeric (polyacrylonitrile (PAN)) nanofibers. Since exciton formation and sustainable electron–hole separation have a vital importance for realizing better solar energy in photovoltaic and photocatalytic devices, we achieved visible light photocatalysis by Pd nanocube decoration onto well designed core–shell nanofibers of ZnO@PAN-NF. By controlling the cubic Pd nanoparticle size and the thickness of the crystalline ZnO nanolayer deposited onto electrospun PAN nanofibers via atomic layer deposition (ALD), defect mediated visible light photocatalysis efficiency can be increased. By utilizing nanofabrication techniques such as thermal decomposition, electrospinning and ALD, this fabricated template became an efficient, defect mediated, Pd nanocube plasmon enhanced photocatalytic system. Due to the enhanced contact features of the Pd nanocubes, an increase was observed for the visible light photocatalytic activity of the flexible and nanofibrous mat of Pd@ZnO@PAN-NF.