A highly porous cryogel is prepared and subsequently functionalized with an atom transfer radical polymerization (ATRP) initiator at the surface. Two new glycomonomers are introduced, which possess deprotected mannose as well as glucose moieties. These are copolymerized with N-isopropylacrylamide (NiPAm) from the cryogel surface, providing a highly hydrophilic porous material, which is characterized by SEM, FT-IR spectroscopy, and NMR spectroscopy. This functionalized support can be applied for affinity chromatography of whole cells owing to the high pore space and diameter. Such an application is exemplified by investigating the ability to capture Escherichia coli bacteria, revealing selective binding interactions of the bacteria with the mannose glycopolymer-functionalized cryogel surface. Thus, the presented glycopolymer-cryogel represents a promising material for affinity chromatography or enrichment of cells.