Perovskite-type cobaltates in the system La2Co1+z(MgxTi1-x)1-zO6 were studied for z=0?x?0.6 and 0?xoC. The space group symmetry of the structure changes from P21/n via Pbnm to R3-bar c with both increasing Mg content and increasing Co content. The La2Co(MgxTi1-x)O6 (z=0) compounds show anti-ferromagnetic couplings of the magnetic moments for the Co below 15 K for x=0, 0.1 and 0.2. XANES spectra show for the compositions 0?x?0.5 a linear decrease in the L3/(L3+L2) Co-L2,3 edge branching ratio with x, in agreement with a decrease of the average Co ion spin-state, from a high-spin to a lower-spin-state, with decreasing nominal Co2+ ion content. -- Graphical abstract: XRPD patterns for perovskite compounds along the lines La2Co(MgxTi1-x)O6 and La2Co1+z(Mg0.5Ti0.5)1-zO6. Display Omitted Research Highlights: ?Tuning of the oxidation state of Co in the perovskite system La2Co1+z(Mtem La2Co1+z(MgxTi1-x)1-zO6, z=0?x?0.6 and ...