Spin-polarized ion scattering spectroscopy using an electron-spin-polarized 4 He + ion beam was developed as a novel analytical method of the element selective spin state at outermost surfaces. Spin-polarized He + ions were generated from the Penning ionization of metastable He 2 3 S1 atoms (He*), which were spin-polarized by optical pumping (OP). The spin polarization of He* (PHe*) was observed to be the highest with an OP radiation density of about 0.05 W cm -2 , and a further increase of the OP radiation density reduced PHe*. This decrease of PHe* is attributed to imperfect polarization of the OP radiation, hence optimization of the OP radiation density is essential to obtain He + ions with high spin polarization. As a result of this optimization, we successfully observed the spin dependence of the scattered He + ion yield on an Fe(100) surface exposed to an oxygen atmosphere.