La2NiO4+δ (LN)-coated PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) composite cathode, designated as PBSCF-LN, for the intermediate temperature solid oxide fuel cells (IT-SOFCs) is prepared by solution infiltration, and investigated comparatively with single phase PBSCF cathode in the half and full cells using Ag and/or Pt paste as the current collector. Compared with Pt, Ag current collector results in a decrease of cathode polarization resistance (RP) by an order of magnitude, which suggests that Ag is electrocatalytically active and not suitable for the use of studying the cathode performance of IT-SOFCs. The RP value of PBSCF-LN cathode is significantly lower than that of PBSCF cathode, no matter whether Pt or Ag current collector is used for the measurement. High power densities ranging from 0.24 to 0.94 W cm−2 at temperatures between 600 and 750 °C are achieved using a full cell with PBSCF-LN cathode. Upon exposure to a CO2-rich atmosphere, carbonate particles are formed on the surface of PBSCF cathode, causing irreversible degradation of electrochemical performance. In contrast, the surface of PBSCF-LN cathode remains clean, and its performance degradation due to CO2 adsorption is recoverable.