Here, we investigate the feasibility of using a liquid plasma spray process as a novel method for the cost-effective fabrication of a nanonetwork of La0.4Sr0.6Co0.2Fe0.8O3−δ (LSCF) and Ce0.8Gd0.2O2−δ (GDC) composite as a high-performance cathode for intermediate-temperature solid oxide fuel cells. A suspension containing well-dispersed nanosized GDC particles in an LSCF precursor solution is designed as the feedstock. The effects of GDC concentration in the suspension on the phase composition, microstructure, and electrochemical performance of the resulting cathode are studied. When the GDC concentration increases to 15 g L−1, the nanosized GDC particles distribute uniformly and continuously on the LSCF backbone to form a porous network structure. The electrochemical studies further indicate that the cathode polarization decreased with the increase in GDC concentration from 0 g L−1 to 15 g L−1, whereas a further increase in the GDC concentration increases the cathode polarization instead. At 600 and 750 °C, the cathode prepared using 15 g L−1 GDC concentration exhibits an impressive area-specific polarization resistance (Rp) of 0.1 Ω cm2 and 0.009 Ω cm2, respectively. Finally, the Rp of the optimal cathode almost does not change after the isothermal dwelling at 650 °C for 350 h.