Perovskite-type compounds of general formula LaMn 1؊x Cu x O 3 and LaCo 1؊x Cu x O 3 (x ؍ 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared by calcining the citrate gel precursors at 823, 923, and 1073 K. The decomposition of the precursors was followed by thermal analysis and the oxides were investigated by means of elemental analysis (atomic absorption and redox titration), Xray powder di4raction, BET surface area, X-ray absorption (EXAFS and XANES), electron microscopy (SEM and TEM), and magnetic susceptibility. LaMn 1؊x Cu x O 3 samples are perovskite-like single phases up to x ؍ 0.6. At x ؍ 0.8 CuO and La 2 CuO 4 phases are present in addition to perovskite. For x ؍ 1.0 the material is formed by CuO and La 2 CuO 4 . Mn(IV) was found by redox titration in all Mn-based perovskite samples, its fraction increasing with the increase in copper content. EXAFS and XANES analyses con5rmed the presence of Mn(IV). Cation vacancies in equal amounts in the 12-coordinated A and octahedral B sites are suggested in the samples with x ؍ 0.0 and x ؍ 0.2, while for x ؍ 0.6 anionic vacancies are present. Materials with su7ciently high surface area (22+36 m 2 g ؊1 for samples 5red at 923 K and 14+22 m 2 g ؊1 for those 5red at 1073 K) were obtained. Crystallite sizes in the ranges 390+500 and 590+940 A s for samples calcined at 923 and 1073 K, respectively, were determined from the FWHM of the (102) X-ray di4raction peak. TEM patterns of LaMnO 3 showed almost regular hexagonal prismatic crystals with sizes of the same order of magnitude (800 A s ) of those drawn from X-ray di4raction, while no evidence of defect clustering was drawn out from TEM and electron di4raction images. For the sample with x ؍ 0.6, TEM and electron di4raction patterns revealed perturbation of the structure. Magnetic susceptibility studies show a ferromagnetic behavior that decreases with increase in x. LaCo 1؊x Cu x O 3 samples are perovskite-like single phases up to x ؍ 0.2. For x ؍ 0.4 a small amount of La 2 CuO 4 , in addition to perovskite, is detected. For x50.6 massive formation of La 2 CuO 4 and CuO is observed. Only trivalent cobalt is found by