In the present study, polystyrene (PS) nanowires in aqueous dispersion with a diameter ranging from 120 to 300 nm are prepared via electrospun and dispersed in water. Relatively, PS nanowires confined in anodic aluminum oxide (AAO) template are prepared through drawing PS flow into the tube of AAO template. Scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) are used to characterize the size of the resultant nanowires and ensure the successful preparation of nanowires. Moreover, the glass transition and physical aging behaviors of the PS nanowires in aqueous dispersion and confined in AAO template are investigated by differential scanning calorimetry (DSC). The PS nanowires in aqueous dispersion and confined in AAO template exhibit different glass transition and physical aging behaviors.