The concept of vectorial spin analysis in spin and angle resolved photoemission is illustrated in this report. Two prototypical systems, Bi/Ag(111• , which show a large Rashba type spin-orbit splitting, were investigated by means of spin and angle resolved photoemission. The spin polarization vectors of individual bands are determined by a twostep fitting routine. First, the measured intensities are fitted with an appropriate number of suitable peaks to quantify the contributions of the individual bands, then the measured spin polarization curves are fitted by varying for each band the polarization direction and its magnitude. We confirm that the surface states experience a large spin splitting. Moreover, we find that all surface state bands are 100 percent spin polarized, and that for some states spin polarization vectors rotate out of the surface plane.