Spin-split energy band structure appears in the surface state due to a broken space inversion symmetry at the surface boundary as well as a strong spin-orbit coupling. Spin- and angle-resolved photoemission spectroscopy (spin-resolved ARPES) has been applied to the study of the spin-split energy band structures of non-magnetic solid surfaces. First of all, some explanation of the spin-splitting mechanism for free electrons, so-called Rashba effect, will be given. Next, our spin-resolved ARPES system equipped with the compact Mott-type spin polarimeter will be introduced. We will show how the surface Rashba effect is observed from the spin-resolved ARPES with the recent result for the surface states of Bi(111). Here, we have observed strong and anti-symmetric spin polarizations with respect to the center of surface Brillouin zone in the surface states of Bi(111).