The flow behavior of a commercial polymeric monolith was investigated by direct numerical simulations employing the lattice-Boltzmann (LB) methodology. An explicit structural representation of the monolith was obtained by serial sectioning of a portion of the monolith and imaging by scanning electron microscopy. After image processing, the three-dimensional structure of a sample block with dimensions of 35.6 μm × 35.6 μm × 27.9 μm was obtained, with uniform 18.5 nm voxel size. Flow was simulated on this reconstructed block using the LB method to obtain the velocity distribution, and in turn macroscopic flow properties such as the permeability and the average velocity. The computed axial velocity distribution exhibits a sharp peak with an exponentially decaying tail. Analysis of the local components of the flow field suggests that flow is not evenly distributed throughout the sample geometry, as is also seen in geometries that exhibit preferential flow paths, such as sphere pack arrays with defects. A significant fraction of negative axial velocities are observed; the largest of these are due to flow along horizontal pores that are also slightly oriented in the negative axial direction. Possible implications for mass transfer are discussed.