Composites of nanoparticles and nanofibers have novel properties that are attractive for many applications, such as a new generation of Lithium ion batteries. The complimentary attributes of these materials are the role of the nanoparticles as active sites and the structural integrity of the nanofibers. In this study, polyacrylonitrile (PAN) nanofibers containing silica nanoparticles are prepared by electrospinning. The composite fibers are electrospun using single and coaxial needle arrangements. The compositions and rheological properties of the precursor solutions are varied to examine the effects on the morphology of the spun fibers and the distribution of silica. The role of silica surface functionality on its distribution within the spun fibers is also discussed.