Recent progress in combing multiple materials with distinct optical, electronic, and thermomechanical properties monolithically in a kilometer-long fiber drawn from a preform offers unique multifunctionality at a low cost. A wide range of unique in-fiber devices have been developed in fiber form-factor using this strategy. Here, I summary my recent results in this nascent field of 'multimaterial fibers'. I will focus on my achievements in producing robust infrared optical fibers and in appropriating optical fiber production technology for applications in nanofabrication. The development of optical components suitable for the infrared (IR) is crucial for applications in this spectral range to reach the maturity level of their counterparts in the visible and near-infrared spectral regimes. A critical class of optical components that has yet to be fully developed is that of IR optical fibers. Here I will present several unique approaches that may result in low-cost, robust IR fibers that transmit light from 1.5 microns to 15 microns drawn from multimaterial preforms. These preforms are prepared exploiting the newly developed procedure of multimaterial coextrusion, which provides unprecedented flexibility in material choices and structure engineering in the extruded preform. I will present several different 'generations' of multimaterial extrusion that enable access to a variety of IR fibers. Examples of the IR fibers realized using this methodology include single mode IR fibers, large index-contrast IR fibers, IR imaging fiber bundles, IR photonic crystal and potentially photonic band-gap fibers. The complex structures produced in multimaterial fibers may also be used in the fabrication of micro- and nano-scale spherical particles by exploiting a recently discovered in-fiber Plateau-Rayleigh capillary instability. Such multimaterial structured particles have promising application in drug delivery, optical sensors, and nanobiotechnology. The benefits accrued from the multimaterial fiber methodology allow for the scalable fabrication of micro- and nano-scale particles having complex internal architectures, such as multi-shell particles, Janus-particles, and particles with combined control over the radial and azimuthal structure. Finally, I will summarize my views on the compatibility of a wide range of amorphous and crystalline materials with the traditional thermal fiber drawing process and with the more recent multimaterial fiber strategy.