Multimaterial fibers engineered to integrate glasses, metals, semiconductors, and composites found applications in ubiquitous sensing, biomedicine, and robotics. The longitudinal symmetry typical of fibers, however, limits the density of functional interfaces with fiber-based devices. Here, thermal drawing and photolithography are combined to produce a scalable method for deterministically breaking axial symmetry within multimaterial fibers. Our approach harnesses a two-step polymerization in thiol–epoxy and thiol–ene photopolymer networks to create a photoresist compatible with high-throughput thermal drawing in atmospheric conditions. This, in turn, delivers meters of fiber that can be patterned along the length increasing the density of functional points. This approach may advance applications of fiber-based devices in distributed sensors, large area optoelectronic devices, and smart textiles.