High resolution synchrotron and neutron single crystal diffraction data of 18-crown-6:(pentakis)urea measured at 30 K are combined, with the aim to better appreciate the electrostatics associated with intermolecular interactions in condensed matter. With two 18-crown-6 molecules and five different urea molecules in the crystal, this represents the most ambitious combined X-ray/synchrotron and neutron experimental charge density analysis to date on a co-crystal or host-guest system incorporating such a large number of unique molecules. Dipole moments of the five urea guest molecules in the crystal are enhanced considerably compared with values determined for isolated molecules, and 2D maps of the electrostatic potential and electric field show clearly how the urea molecules are oriented with dipole moments aligned along the electric field exerted by their molecular neighbors. Experimental electric fields in the range 10-19 GV m-1 , obtained for the five different urea environments, corroborate independent measurements of electric fields in the active sites of enzymes, and provide an important experimental reference point for recent discussions focused on electric-field-assisted catalysis.