Nanostructured perovskite-type oxides LnFeO3 (Ln = La, Nd, Gd, Yb, Ho, Lu) were prepared using a method of high-temperature solid state reactions. The effects of lanthanides substitution at the A-site on the catalytic performance of the complex oxides during the dry reforming of methane (DRM) were investigated. It was found that there is a correlation between the nature of the element in A-site of perovskite and its catalytic performances (CH4 and CO2 convention, CO and H2 formation rate). Moreover, the “gadolinium angle” was established in products formation rate, which was related to the features of changing the electronic configuration in lanthanide series. © 2019 Bulgarian Academy of Sciences, Union of Chemists in Bulgaria.