Bioinspired vascular networks transport heat and mass in hydrogels, microfluidic devices, self-healing and self-cooling structures, filters, and flow batteries. Lengthy, multistep fabrication processes involving solvents, external heat, and vacuum hinder large-scale application of vascular networks in structural materials. Here, we report the rapid (seconds to minutes), scalable, and synchronized fabrication of vascular thermosets and fiber-reinforced composites under ambient conditions. The exothermic frontal polymerization (FP) of a liquid or gelled resin facilitates coordinated depolymerization of an embedded sacrificial template to create host structures with high-fidelity interconnected microchannels. The chemical energy released during matrix polymerization eliminates the need for a sustained external heat source and greatly reduces external energy consumption for processing. Programming the rate of depolymerization of the sacrificial thermoplastic to match the kinetics of FP has the potential to significantly expedite the fabrication of vascular structures with extended lifetimes, microreactors, and imaging phantoms for understanding capillary flow in biological systems.