Quantifying the connectivity of material microstructures is important for a wide range of applications from filters to biomaterials. Currently, the most used measure of connectivity is the Euler number, which is a topological invariant. Topology alone, however, is not sufficient for most practical purposes. In this study, we use our recently introduced connectivity measure, called the contour tree connectivity (CTC), to study microstructures for flow analysis. CTC is a new structural connectivity measure that is based on contour trees and algebraic graph theory. To test CTC, we generated a dataset composed of 120 samples and six different types of artificial microstructures. We compared CTC against the Euler parameter (EP), the parameter for connected pairs, the nominal opening dimension (d nom ) and the permeabilities estimated using direct pore scale modelling. The results show that d nom is highly correlated with permeability (R 2 ¼ 0.91), but cannot separate the structural differences. The groups are best classified with feature combinations that include CTC. CTC provides new information with a different connectivity interpretation that can be used to analyse and design materials with complex microstructures.