Abstract: The study investigated how alloying with Ce and cold rolling affect the activation behavior of V70Ti10Cr20-based alloys. Activation conditions for cold rolled samples alone (V70Ti10Cr20-0.3) and substituted Ce samples alone (V70Ti10Cr20-Cex) were reduced to one heat treatment and incubation time of approximately 105 min, respectively. Unexpectedly, the two modification methods produce excellent synergistic effects that the co-modified sample (V70Ti10Cr20Ce1-0.3) was activated at room temperature without incubation period, and reached saturation capacity (4wt%) within 18 min. Further studies show that CeO2 formed through Ce doping, serves as an active site for hydrogen absorption, facilitating the passage of hydrogen atoms through the dense oxide layer on the surface of V-based alloys. Upon the foundation of Ce doping, cold rolling leads to the aggregation of dislocations around CeO2 sites, thereby further establishing a hydrogen diffusion pathway from the surface into the bulk phase, thus significantly improving the activation performance of the alloy. This work establishes a robust basis for the practical engineering use of vanadium-based hydrogen storage alloys.