Dramatic and rapid changes in the intensity and spectrum of light under water at dusk and dawn are well known, but reports regarding the light's polarization at these periods are sparse. Using a rapid spectropolarimeter, we examined the spatial and spectral characteristics of the underwater polarization patterns from sunrise to midday and compared them with a Rayleigh-based model for e-vector orientation and percent polarization. With the Sun near the horizon, the underwater polarization patterns were distinctive. Unlike the polarization at small solar zenith angles, the underwater polarization at large solar zenith angles cannot be predicted by simple Rayleigh scattering, most likely because of the relatively high contribution of skylight. At sunrise, the underwater polarization pattern outside of Snell's window differed from that found during the day in percent polarization, spatial distribution, and wavelength dependence. These unique polarization characteristics may provide a polarization-sensitive animal with a distinct cue for mediating dial vertical migration performed by plankton or with another timing signal.