Stable electrode materials with guaranteed long-term cyclability are indispensable for advanced lithium-ion batteries. Recently, delafossite CuFeO2 has received considerable attention, due to its relative structural integrity and cycling stability. Nevertheless, the low conductivity of delafossite and its relatively low theoretical capacity prevent its use as feasible electrodes for next-generation batteries that require higher reversible capacities. In this work, we suggest a simple and straightforward approach to prepare CuFeO2-NiFe2O4 by introducing Ni precursor into Cu and Fe precursor to form NiFe2O4, which exhibits higher capacity but suffers from capacity fading, through sol-gel process and subsequent heat treatments. The presence of both NiFe2O4 and CuFeO2 is apparent, and the heterostructure arising from the formation of NiFe2O4 within CuFeO2 renders some synergistic effects between the two active materials. As a result, the CuFeO2-NiFe2O4 hybrid sample exhibits excellent cycling stability and improved rate capability, and can deliver stable electrochemical performance for 800 cycles at a current density of 5.0 A g(-1). This work is an early report on introducing a foreign element into the sol-gel process to fabricate heterostructures as electrodes for batteries, which open up various research opportunities in the near future.