Giant magnetoresistance (GMR) behavior in electrodeposited NFe/Cu/Ni multilayered (ML) structures is investigated as a function of non-magnetic (Cu) and ferromagnetic (Fe and Ni) layers' thicknesses. Detailed structural and magnetic analyses of the ML structures are studied before looking into the GMR behavior. Structural analyses reveal that all peaks are well matched with Ni (face-centered cubic) being the top most layer during ML deposition. Shifting of preferred orientation, between (220) and (111) planes, is observed with the thickest layer of copper spacer. Refined structural parameters are calculated and details of fittings are discussed with reference to layer thicknesses. Crystallite size, dislocation density, stacking fault probability, and strain all show oscillatory behavior with variation in thicknesses. Magnetic behavior shows strong dependence of magnetization on thickness of each layer. Saturation magnetization (<inline-formula> <tex-math notation="LaTeX">M_{s}) </tex-math></inline-formula> increases up to a value of 10.12 emu/cm 3 with increasing Fe and Ni layer thicknesses. Whereas, oscillatory behavior of magnetization is observed with variation in Cu layer thickness. Magnetoresistance (MR) measurements show oscillatory GMR behavior as a function of intervening layer thickness. Highest value of GMR ~12% is observed at a Cu layer thickness of 9.6 nm. Structural, magnetic, and MR properties of NFe/Cu/Fe are observed on the basis of variation of thicknesses of non-magnetic (Cu) and ferromagnetic (Fe and Ni) layers. It is observed that layer thicknesses play a dominant effect on the nature (i.e., oscillatory) and on the value of GMR.