Sodium atoms (108–1011cm−3) effused from an oven were stepwise excited from their ground state to a Rydberg statensornd(20≤n≤26) by two pulsed dye lasers (∼5–10 ns, ∼100 &mgr;J, ∼1.6‐mm‐diam spot). The laser energy density necessary to saturate the excitation processes from the ground state to the Rydberg state is ∼ several mJ/cm2. About 50 ns after the laser irradiation, a pulsed electric field (0.5–5.5 kV/cm) was applied to the Rydberg atoms to ionize them and accelerate the resulting ions. Thus, a pulsed sodium ion beam of purity >99.99% was obtained with a maximum total electric charge of ∼5 pC and a pulse width of ∼120 ns full width at half maximum. The total electric charge of the ion beam is estimated including the effect of space‐charge field of the beam ions, and is in good agreement with the experimental values.