Hollow Silica (SiO2) fibers with porous walls were synthesized by a coaxial electrospinning method. The SiO2 sol prepared by a sol–gel route was blended with polyvinylacetate to prepare precursor solutions for electrospinning. Electrospinning-synthesized hollow SiO2 fibers were highly porous with pore diameters of ~45 nm. A slow heating rate <5°C/min during calcination was required to sustain the hollow and porous morphology. In addition, aligned hollow SiO2 fibers were successfully synthesized using a separate electrode configuration.