The molecular configuration and intermolecular arrangement of polycrystalline methoxycarbonylurea (MCU) has been studied by a combination of chemical editing, rotational echo double resonance (REDOR) spectroscopy and ab initio calculations. From the multispin IS(n) REDOR experiments several dipolar couplings were determined and converted into distance constraints. Intra- and intermolecular dipolar couplings were distinguished by isotope dilution. The configuration of the MCU molecule can be determined from three torsion angles Psi1, Psi2, and Psi3. Ab initio calculations showed that these angles are either 0 degrees or 180 degrees (Z or E). From the REDOR experiments, the E configuration was found for Psi1 and Psi2 and the Z configuration for Psi3. Thus the configuration of MCU in the solid state was determined to be EEZ. Distance constraints for the intermolecular arrangement of MCU were obtained by performing REDOR experiments on 13C15N2 MCU with different degrees of isotope dilution and on a cocrystallized 1:1 mixture of 13C(urea) MCU and 15N(amide) MCU. By combining these distance constraints with molecular modeling, three different possible packing motifs for MCU molecules were found. The molecules in these motifs are arranged as linear chains with methoxy groups at the borders of the chains. All the intermolecular hydrogen bond donors and acceptors in the interior of the chain are saturated.