A freely oscillating torsion pendulum has been used to characterize the dynamic mechanical behavior of single polymer-coated optical fibers. The dynamical mechanical spectra of the polymer coatings exhibit a glass transition temperature (Tg), a cryogenic glassy-state relaxation (Tsec), and another cryogenic relaxation that is attributed to water present in the coating (TH2O). The shear modulus (G′) of the coating was computed from the shear moduli of the composite specimen and the core, assuming that the coating and core deform through the same angle on oscillation. The glassy-state modulus was the same for both thin and thick coatings, although the intensity of the damping peaks, as measured by the logarithmic decrement, increased with coating thickness. Comparison of the dynamic mechanical behavior of a coated optical fiber and of a free film cast from the same reactive components shows that the polymer itself can absorb water at ambient conditions and display a mechanical relaxation at cryogenic temperatures. The T., H2O and Tsec relaxations are coupled with respect to their intensities. Latent chemical reactivity was found in one coating above its maximum temperature of cure. In this, the temperature of cure determines the glass transition temperature.