Nano-to micrometer-sized surface defects on UV-grade fused silica surfaces are known to be effectively smoothed through the use of high-temperature localized CO2 laser heating, thereby enhancing optical properties. However, the details of the mass transport and the effect of hydroxyl content on the laser smoothing of defective silica at sub-micron length scales are still not completely understood. In this study, we examine the morphological evolution of sub-micron, dry-etched periodic surface structures on type II and type III SiO2 substrates under 10.6 mm CO2 laser irradiation using atomic force microscopy (AFM). In situ thermal imaging was used to map the transient temperature field across the heated region, allowing assessment of the T-dependent mass transport mechanisms under different laser-heating conditions. Computational fluid dynamics simulations correlated well with experimental results, and showed that for large effective capillary numbers (N-c > 2), surface diffusion is negligible and smoothing is dictated by capillary action, despite the relatively small spatial scales studied here. Extracted viscosity values over 1700-2000 K were higher than the predicted bulk values, but were consistent with the surface depletion of OH groups, which was confirmed using confocal Raman microscopy. Published by Elsevier B. V.