The structure of fluorinated alcohols is a matter of considerable interest in view of wide-ranging biomolecular applications. The micro heterogeneity of fluorinated alcohols in the liquid state, in particular, has been a matter of debate and discussion in recent years using experimental and theoretical methods, including neutron or X-ray diffraction, as well as density functional theory (DFT) and molecular dynamics (MD) simulations. Here, we show that H-1 and F-19 Overhauser dynamic nuclear polarization (ODNP) buildup curves in solution state at room temperature show unusual behavior that could offer a novel approach to investigate the structural heterogeneity and dynamics of such homogeneous liquids with improved sensitivity. A detailed analysis of multiexponential ODNP buildup curves as a function of microwave irradiation time is shown to evidence microheterogeneity in such systems. Experimental ODNP buildup rates are interpreted using simple motional models that yield the motional correlation times of the relevant species in solution. It may be emphasized that this information is not available from standard approaches of high-resolution nuclear magnetic resonance (NMR) spectroscopy. While the present study focuses on fluorinated alcohols, it is to be anticipated that this approach would be valuable in the study of molecular assemblies in the solution state, including peptides, surfactant systems, etc.