We prepared titanium dioxide/PVA nanocomposite fiber webs for application in multifunctional textiles by electrospinning. The morphological properties of the TiO₂/PVA nanocomposite fibers were characterized using scanning electron microscopy and transmission electron microscopy. Layered fabric systems with electrospun TiO₂ nanocomposite fiber webs were developed using various concentrations of TiO₂ and a range of web area densities, and then the UV‐protective properties, antibacterial functions, formaldehyde decomposition ability, and ammonia deodorization efficiency of the fabric systems were assessed. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 2 wt% TiO₂ nanoparticles at 3.0 g m⁻² web area density exhibited an ultraviolet protection factor of greater than 50, indicating excellent UV protection. The same system showed a 99.3% reduction in Staphylococcus aureus. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m⁻² web area density exhibited a 85.3% reduction in Klebsiella pneumoniae. Titanium dioxide nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m⁻² web area density exhibited a formaldehyde decomposition efficiency of 40% after 2 h, 60% after 4 h, and 80% after 15 h under UV irradiation. The same system showed an ammonia deodorization efficiency of 32.2% under UV irradiation for 2 h. These results demonstrate that TiO₂ nanocomposite fibers can be used to produce advanced textile materials with multifunctional properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012