Seed germination is the critical initial phase in the life cycle of plant and it is affected by various exogenous factors, including heavy metals. Seed germination and subsequent seedling growth of alfalfa (Medicago sativa L.) incubated in glass Petri dish in presence of elevated concentrations of pentavalent vanadium V(V) solution (0, 0.1, 0.5, 2, 4, 10, 50 mg L−1 V, supplied as NaVO3·2H2O) were evaluated. Results showed that vanadium did not (P > 0.05) affect seed germination, final survival rate, and seedling height of alfalfa when exogenously treated dosages were ≤ 10 mg L−1 V, whereas the root vitality and root elongation were distinctly inhibited at ≥ 0.5 mg L−1 V treatments. A progressively deepened testa color at increasing vanadium concentrations during germination and an apparent modified structure of the seed coat at 50 mg L−1 V compared to control in alfalfa were noted. Alfalfa seeds showed rapid and almost synchronous radicle emergence, independently of the vanadium concentration in the medium. The accumulation of vanadium in testa is beneficial to alleviate its toxicity to the seed germination of alfalfa. Leaf proline content was dramatically increased at ≥ 0.5 mg L−1 V treatments compared with the control. Emerged seedlings displayed enough vigor and health to potentially colonize in the vanadium-contained matrix. Thus, alfalfa represents a good candidate for phytoremediation approach aimed at decontaminating environments when vanadium concentrations are within the determined thresholds.