Building two-dimensional (2D) and three-dimensional (3D) micro- and nanofibril structures with designable patterns and functionalities will offer exciting prospects for numerous applications spanning from permeable bioelectronics to tissue engineering scaffolds. This Spotlight on Applications highlights recent technological advances in fiber printing and patterning with functional materials for biointerfacing applications. We first introduce the current state of development of micro- and nanofibers with applications in biology and medical wearables. We then describe our contributions in developing a series of fiber printing techniques that enable the patterning of functional fiber architectures in three dimensions. These fiber printing techniques expand the material library and device designs, which underpin technological capabilities from enabling fundamental studies in cell migration to customizable and ecofriendly fabrication of sensors. Finally, we provide an outlook on the strategic pathways for developing the next-generation bioelectronics and "Fiber-of-Things" (FoT) using nano/micro-fibers as architectural building blocks.