Sub-100 nm resolution local thermal analysis, X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements were used to relate surface polymer distribution with the composition of electrospun fiber mats and spin coated films obtained from aqueous dispersions of lignin, polyvinyl alcohol (PVA), and cellulose nanocrystal (CNC). Defect-free lignin/PVA fibers were produced with radii which were observed to increase with lignin concentration and with the addition of CNCs. XPS and WCA results indicate a nonlinear relationship between the surface and the bulk compositions. A threshold around 50 wt % bulk composition was identified in which extensive partitioning of PVA and lignin components occurred on the surface below and above this value. In 75:25 wt % lignin/PVA solvent cast films, phase separated domains were observed. Using nanoscale thermal analyses, the continuous phase was determined to be lignin-rich and the discontinuous phase had a lignin/PVA dispersion. Importantly, the size of the phase separated domains was reduced by the addition of CNCs. When electrospun fiber surfaces were lignin-rich, the addition of CNCs affected their surfaces. In contrast, no surface effects were observed with the addition of CNCs in PVA-rich fibers. Overall, we highlight the importance of molecular interactions and phase separation on the surface properties of fibers from lignin as an abundant raw material for the fabrication of new functional materials.