The crystal structures of three polymorphs found for the addition complex of urea and barbituric acid are described and compared. Two polymorphs are monoclinic, space groups P2(1)/c and Cc, whereas the third is triclinic, P1. The displacement of electron density towards the mesomeric forms, corresponding to the tautomeric forms of higher stability, of the barbituric acid molecule seem to influence the type of hydrogen bonds formed, which in turn determines the different packing topology in the polymorphs. While the polymorphic forms can be easily differentiated at the first-level graph-set analysis of their hydrogen-bonding patterns, a higher-level analysis enables important features of the mutual spatial arrangement of the structural components to be revealed.