© 2017 Wiley Periodicals, Inc. Three-dimensional polymer nanofibrous mats with tunable wettability have been fabricated using a single step non-conductive template assisted electrospinning process. Cellulose acetate nanofibers are electrospun over a nylon mesh, which acts as the template. The as-deposited fiber mat is removed from this template to produce a free standing three-dimensional micropatterned nanofibrous mat. By simply varying the template mesh dimensions, the fraction of the air-liquid interface can be changed which allows control of the wetting mechanics. It is shown that the water contact angle can be varied from about 30° for a planar network to about 140° for a patterned mat implying a complete transition from hydrophilic to hydrophobic behavior. Furthermore, upon stretching the fiber mat loses its pattern irreversibly and reducing the contact angle from 140° to 110° with increasing stretching. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44709.