The magnetic exchange constants of vanadyl pyrophosphate (VO)(2)P(2)O(7) have been calculated on the basis of a combined DFT/broken symmetry approach. The three reported phases, ambient-pressure orthorhombic, ambient-pressure monoclinic, and high-pressure orthorhombic, have been explicitly considered. Calculations have been performed on four types of model clusters extracted from the crystal lattices. The singularity of each phase is clearly reflected through the number and values of exchange parameters. Our results show that the exchange interactions can be described in first approximation within the alternating antiferromagnetic chain model. The largest exchange coupling along the chain occurs through O-P-O bridges. The interchain interactions are much weaker and are of ferromagnetic nature.