To understand the relationship between mechanical behavior and fiber assembly in electrospun ceramic-based fibrous mats, the tensile performance of silica, silica/polydimethylsiloxane and silica/polymethyl methacrylate hybrid fibrous mats was investigated. Elastic-plastic behavior as a whole was confirmed in the silica-based fibrous mats. The initial isotropy and disordered networks with point contact between the randomly oriented fibers before the tensile test and the highly oriented fibrous bundles with side contact between the aligned fibers after the tensile test were observed using scanning electron microscopy.