In this paper, with the example of two different polymorphs of KEu(MoO4)(2), the influence of the ordering of the A-cations on the luminescent properties in scheelite related compounds (A',A '') (B',B '')O-4 is investigated. The polymorphs were synthesized using a solid state method. The study confirmed the existence of only two polymorphic forms at annealing temperature range 923-1203 K and ambient pressure: a low temperature anorthic alpha-phase and a monoclinic high temperature beta-phase with an incommensurately modulated structure. The structures of both polymorphs were solved using transmission electron microscopy and refined from synchrotron powder X-ray diffraction data. The monoclinic beta-KEu(MoO4)(2) has a (3+1)-dimensional incommensurately modulated structure (superspace group I2/b(alpha beta 0)00, a = 5.52645(4) angstrom, b = 5.28277(4) angstrom, c = 11.73797(8) angstrom, gamma = 91.2189(4)degrees, q = 0.56821(2)a*-0.12388(3)b*), whereas the anorthic alpha-phase is (3+1)-dimensional commensurately modulated (superspace group I (1) over bar(alpha beta gamma)0, a = 5.58727(22) angstrom, b = 5.29188(18)angstrom, c = 11.7120(4) angstrom, alpha = 90.485(3)degrees, beta = 88.074(3)degrees, gamma = 91.0270(23)degrees, q = 1/2a* + 1/2c*). In both cases the modulation arises due to Eu/K cation ordering at the A site: the formation of a 2-dimensional Eu3+ network is characteristic for the alpha-phase, while a 3-dimensional Eu3+-framework is observed for the beta-phase structure. The luminescent properties of KEu(MoO4)(2) samples prepared under different annealing conditions were measured, and the relation between their optical properties and their structures is discussed.