Li-ion hybrid capacitors (LIHCs) as a novel and promising energy storage unit, consisting of a Li-ion battery type anode and an electrochemical double layer capacitance (EDLC) type cathode, has attracted enormous research attentions. However, it remains a significant challenge to obtain high-performance LIHCs due to most battery-type anodes with the sluggish kinetics of Li-ion storage and low specific capacitance of common capacitor-type cathodes. Thus, it is highly required to design and fabricate novel alternative high-performance battery type anode materials and capacitor-type cathode materials, able to deliver higher energies and power densities in organic electrolyte. In this work, a novel high-performance LIHCs is constructed by combining a Li-ion battery type anode (3D graphene/MoO₃ nanocomposite) with a capacitor type cathode (3D graphene/PANI derived carbon material). Such a subtle design endow LIHCs with a wide voltage range of (3.8 V), a high energy density of 128.3 Wh·kg^-1, and an ultra-long cycle life up to 3000 cycles with 87% capacity retention.