Layered magnetoelectric Ni/PZT/TbFe2 composites have been prepared by electroless deposition and bonding method. The influence of the Ni layer thickness on ME coupling and resonance frequency is discussed. The results show that the magnetoelectric coefficient of Ni/PZT/TbFe2 composites changes differently from that of other composites and two remarkable resonance peaks have been observed. The magnetoelectric voltage coefficient at the first-order longitudinal resonance mode increases as the Ni layer thickness increases. Both experimental and calculated data reveal that the first-order bending resonance frequency fr1 and longitudinal resonance frequency fr2 increase with the Ni layer thickness.