Deformation mechanisms of a ZrTiAlV alloy with two ductile phases including a hexagonal close-packed (hcp) structure phase were investigated. A ZrTiAlV alloy was prepared via smelting, breakdown, forging, and suitable heat treatments. X-ray diffraction results show that the proposed ZrTiAlV alloy has two ductile phase structures, namely, hcp structure α-phase and bcc (body-centered cubic) structure β-phase. Scanning electron microscopy (SEM) results show that the plastic deformation of the examined ZrTiAlV alloy starts from the α-phase. Transmission electron microscopy (TEM) analysis shows that only dislocation slips can be found near fractured areas, and the main slip plane in the α-phase is the (0001) lattice plane. Both of the SEM and TEM results show the inexistence of deformation twin in the examined ZrTiAlV alloy including a hcp structure α-phase. Reasons for the abnormal deformation behavior of the hcp structure α-phase are also discussed.