The structure of the supramolecular complex calcium - trifluoromethanesulfonate - 1,3-di-4-pyridylurea-methanol (1/2/ 2/4), Ca2+.2CF(3)SO(3)(-).2C(11)H(10)N(4)O.4CH(4)O, is presented. The Ca2+ ion lies on an inversion centre and is octahedrally coordinated by four methanol molecules and two trifluoromethanesulfonate counter-ions. The molecular packing is dominated by hydrogen-bonded sheets in the ( 110) plane which contain R-4(4)( 32) rings; in these rings, significant pi-pi interactions are observed between inversion-related 1,3-di-4-pyridylurea molecules.