Chemical looping reforming with water splitting (CLRWS) to coproduce the syngas and high purity hydrogen was investigated using Ni–Fe bimetallic oxygen carriers (OCs). The oxygen carrier with 20 wt% of NiO (termed as Ni20Fe80) was more suitable for CLRWS at 900 °C with a mass ratio of steam to bio-oil (S/B) of 1.2. Under the condition, the syngas exhibited a yield of 1.79 Nm 3 /kg with a H 2 /CO ratio of 2.01 in fuel reactor (FR), meanwhile, the hydrogen presented a yield of 0.70 Nm 3 /kg with a purity of 96.04% in steam reactor (SR). However, the stability of Ni20Fe80 gradually decreased during the cyclic test. Three metal oxide additives, including CeO 2 , Al 2 O 3 and TiO 2 , with a mass fraction of 25 wt%, were used to modify the Ni20Fe80. The corresponding OCs were abbreviated as Ni15Fe60Ce25, Ni15Fe60Al25 and Ni15Fe60Ti25. The Ni15Fe60Ce25 exhibited the best performance during the cyclic test. After 5 cycles, the syngas yield, hydrogen yield and purity were 2.01 Nm 3 /kg, 0.75 Nm 3 /kg and 96.26%, respectively. The Ni15Fe60Al25 has good potential for syngas production, but not suitable for hydrogen production in SR. It was attributed to that the formation of iron-aluminum spinel regulated the lattice oxygen reactivity to favor the syngas production, as well inhibited the reduction of Fe species, which resulted in a low hydrogen yield in SR. • Ni enhanced Fe-based OCs reactivity but aggravated carbon deposition. • Excessive Ni resulted the agglomeration and sintering of Ni–Fe bimetallic OCs. • The syngas with H 2 /CO ratio of 2.0 was obtained at S/B = 1.2 in FR with Ni20Fe80. • The Ni15Fe60Ce25 is suitable for syngas and hydrogen coproduction. • The Ni15Fe60Al25 showed considerable potential in the syngas production.