In the coordination compound poly[diaqua(μ2‐4,4′‐bipyridine)(μ2‐4‐carboxylatocinnamato)nickel(II)], [Ni(C10H6O4)(C10H8N2)(H2O)2]n, both the 4‐carboxylatocinnamate and 4,4′‐bipyridine (4,4′‐bpy) ligands act as bidentate bridges, connecting the NiII centres in an octahedral coordination geometry into a two‐dimensional (4,4) layer. Each layer polycatenates two other identical layers, thus giving a rare 2D → 3D polycatenating network (2D and 3D are two‐ and three‐dimensional, respectively), with a mutually parallel arrangement of the layers. The chiral 4,4′‐bpy ligands link the NiII centres into chiral chains, thus introducing chirality into the layer and the resulting 3D network.