A roller electrospinning technique is combined with sol-gel chemistry to fabricate silica and polymeric materials on conductive and nonconductive substrates to verify its ability for controlling the long-range periodic structure of the final product. According to the experimental results, formation of the one-dimensional periodic silica structure was dependent on the electrical conductivity of the collector substrate. The periodic density seems to be related to the width of silica product. No effect from the electrical conductivity of collector substrate on the structure of polymeric system was observed. An energy transformation model was proposed to investigate the formation mechanism of this periodic structure. The theoretical simulation indicates that large width-to-thickness ratio of the product and high-energy transformation efficiency favor the formation of the long-range periodic structure.