In this work we present a modified citrate-nitrate route using citric acid as a chelating agent as an effective and facile strategy to obtain nanocrystalline La3Ni2O7+δ (L3N2) and La4Ni3O10−δ (L4N3) powders for the preparation of solid oxide fuel cell cathodes. Both samples crystallize in a Fmmm orthorhombic layered Lan+1NinO3n+1 Ruddlesden-Popper structure, with n = 2 and 3, respectively. The oxygen non-stoichiometry, determined by TGA is equal to 0.05 and 0.06 for L3N2 and L4N3, respectively. The thermal expansion coefficient values of L3N2 and L4N3 are 11.0 × 10−6 K−1 and 11.5 × 10−6 K−1, respectively. This study focused on L3N2, L4N3 and on novel composite electrodes with CGO (Ce0.9Gd0.1O2−δ): L3N2-CGO and L4N3-CGO with a view to taking advantage of their complimentary properties, i.e. high ionic conductivity of CGO and high electronic conductivity of Lan+1NinO3n+1 (n = 2 and 3). A significant improvement of the polarization resistance, from 1.0 to 0.03 Ω cm2 and from 1.5 to 0.52 Ω cm2 at 700 °C, is obtained when 50 wt% CGO is added to L3N2 and L4N3, respectively. In addition, the L3N2-CGO composite shows good long-term stability at 900 °C for 2 weeks in air, confirming its suitability as a SOFC cathode.