New microstructures were developed by strong grain refinement and phase control in a Ti–13Nb–13Zr alloy. Ultrafine-grained multiphase alloys were fabricated using a multipass caliber-rolling process at the (α+β) region. Transmission electron microscopy analysis revealed that different types of martensitic transformations occurred depending on the cooling rate. The developed alloys exhibited improved strength and ductility compared with a conventional material, and this enhancement of properties is discussed in terms of microstructural effects on the strain-hardening behavior.