One of impotent materials issues of Ti-Cr-V based hydrogen storage alloys is to improve cyclic degradation of storage capacity, which has been assumed to be the effect of internal stress. We focused on the sub-micron structure of this material, which can be accumulated during cyclic use. We used 24Ti-36Cr-40V alloy for the specimens, after FZ melting. Powered samples were fabricated by mechanical grinding under Ar environment. Vacuum annealing was carried out for reducing residual stress and lattice defects. PCT properties were tested at 293 K under 4.5 MPa. XRD and TEM were carried out for important samples. In the first cycle, the annealing resulted in the increasing of storage capacity, but in the second cycle the improving was disappeared. Comparing microstructures with and without annealing, complex dislocation structures were observed after cyclic hydrogenation. It is notable that dislocation free structure was some time observed in the fine grains of less than 0.1 micron, which suggests the possibility of fine structure without defect accumulation.