Silica monoliths are increasingly used as fixed-bed supports in separation and catalysis because their bimodal pore space architecture combines excellent mass transport properties with a large surface area. To optimize their performance, a quantitative relationship between morphology and transport characteristics has to be established, and synthesis conditions that lead to a desired morphology optimized for a targeted application must be identified. However, the effects of specific synthesis parameters on the structural properties of silica monoliths are still poorly understood. An important question is how far the macropore and domain size can be reduced without compromising the structural homogeneity. We address this question with quantitative morphological data derived for a set of eight macroporous-mesoporous silica monoliths with an average macropore size (d(macro)) between of beeen 3.7 and 0.1 mu m, prepared following an established route involving the sol gel transition and phase separation. The macropore space of the silica monolith samples is reconstructed using focused ion beam scanning electron microscopy followed by a quantitative assessment of geometrical and topological properties based on chord length distributions (CLDs) and branch-node analysis of the pore network, respectively. We observe a significant increase in structural heterogeneity, indicated by a decrease in the parameter k derived from fitting a k-gamma function function to the CLDs, when d(macro) reaches the submicrometer range. The compromised structural homogeneity of silica monoliths with submicrometer macropores could possibly originate from early structural freezing during the competitive processes of sol gel transition and phase separation. It is therefore questionable if the common approach of reducing the morphological features of silica monoliths into the submicrometer regime by changing the point of sol gel transition can be successful. Alternative strategies and a better understanding of the involved competitive processes should be the focus of future research.