Zeta potentials of surfaces bearing stable mono- or multilayers of polyelectrolyte were determined using the spinning disk method recently described by Sides et al. (Langmuir 2004, 20, 11493-11498). In this technique, the streaming potential difference between two electrodes, one at the disk surface, is quantitatively related to zeta potential. Variables such as rotation speed, electrolyte concentration, and electrode distance from the disk surface were explored and used to validate the recently-described theory, which emphasizes minimal contribution to net potential from surface conductivity. Layer-by-layer oscillations in sign and magnitude of the zeta potential were observed, in accord with prior work using electrophoretic mobility of multilayer-coated particles and other streaming potential measurements. The open geometry and the excellent mass transport of the spinning disk allowed in-situ observation of surface charge switching during the addition of a layer. As with all zeta potentials, especially those recorded at soft interfaces, translating results to quantitative densities of fixed surface charge is a challenge.