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EuTi0.5W0.5O3-xNx oxynitrides with nitrogen contents between 0.87 and 1.63 have been synthesized by ammonolysis of EuTi0.5W0.5O4 scheelite at high temperature. They are B-site disordered perovskites that show two different crystal symmetries as a function of the nitrogen content, changing at x near 1.3 from cubic Pm-3m to orthorhombic Pbnm. The nitriding degree is tuned by the ammonia flow rate and synthesis temperature, and determines the oxidation states of the cations and the equilibrium Eu2+ ​+ ​W6+ ↔ Eu3++W5+ promoting the decrease of the tolerance factor and the structural transition for large x values and electronic reconstructions. Accompanying the symmetry lowering, the nature of the magnetic order of Eu2+ moments changes from ferromagnetic to antiferromagnetic as a result of a complex interplay of antiferromagnetic/ferromagnetic superexchange interactions balanced by structural effects and the carrier-mediated magnetic exchange between Eu2+ ions., This work was supported by the Spanish Ministerio de Ciencia, Universidades e Investigación, Spain (Projects MAT2017-86616-R and MAT2017-85232-R and from Generalitat de Catalunya (2017SGR1377, 2017SGR581). ICMAB acknowledges financial support from MINECO through the Severo Ochoa Program (SEV-2015-0496). We thank Alba synchrotron (Experiment number AV-2017092391) for the provision of beam time; we also thank Dr. François Fauth for assistance during data collection and Dr. Bernat Bozzo (ICMAB-CSIC) for performing the magnetic measurements.