While artificially encoded microfibers inspired by biosynthetic fibrous microstructures are drawing considerable research attention, their practical applications are hindered by multiple limitations. Here, a programmable dynamic interfacial spinning (DIS) process is proposed for producing volume-encoded microfibers with superior encoding capacity and reliability. The produced microfibers comprise a sheath of deformed hydrogel encapsulating sequentially aligned droplets, with their morphologies controllable by adjusting the flow rates of the corresponding fluids and the vibration parameters of the spinning nozzle. In particular, microfibers with volumetric encoding of inner droplet sequence are constructed for information storage and encryption. With appropriate functionalization of volume-encoded microfibers, we have also demonstrated magnetic guidance and selective activation to simulate intravascular drug delivery. Our study implies the potential applications of the volume-encoded microfibers in information communication, drug delivery and biomedical engineering.