In the present work, nickel/nickel oxide/carbon matrix (Ni/NiO@cm) was generated using [Ni(salen)] complex by a facile pyrolysis method. The formation of the Ni/NiO@cm was confirmed by several physico-chemical analyses. Subsequently, the Ni/NiO/cm was explored as anode material for lithium-ion battery in each of half-cell and full-cell. The CR2032-type lithium-ion half-cell (Ni/NiO@cm∣LiPF6∣Li) delivered a stabilized discharge capacity of 330 mAh g−1 with excellent cycling stability (200 cycles) as well as Columbic efficiency. The stable lithium-ion storage performance of the Ni/NiO@cm anode is attributed to the occurrence of conversion/re-conversion reactions. The presence of the carbon matrix acted as both conductive network as well as cushion during volume change. Consequently, the lithium storage performances of the Ni/NiO@cm as anode was verified in the form of CR2032-type full-cell that exhibted discharge capacity of 400 mA h g−1 at 0.1C-rate and stabilized capacity of 100 mA h g−1 at high 0.3C-rate for 500 cycles. Even at 500th cycle, the full-cell delivered 70% retention of discharge capacity. A proto-type full cell was demonstrated to power a commercial (3.0 V) green LED bulb for more than 9 h continuously on single charge.