CoFe/Si interfacial structures have been realised by electron beam evaporation of CoFe magnetic alloy on p-and n-Si substrates. These realised interfacial structures have been characterised from X-ray diffraction (XRD), atomic force microscopy (AFM), magnetic force microscopy (MFM) and magnetisation (M-H) characteristics. XRD data have shown the presence of CoFe (bcc phase) and b-FeSi 2 phases for CoFe/p-Si interfacial structures, whereas CoFe/n-Si interfacial structures have shown the presence of CoFe (bcc and fcc) phases along with Fe 3 Si, e-FeSi and b-FeSi 2 silicide phases having nanodimension crystallites. The M-H characteristics have shown the superparamagnetic type behaviour for CoFe/p-Si structure, whereas CoFe/n-Si structure shows a feature of interfacial antiferromagnetic (AF) coupling. The observed magnetic behaviour has been understood due to the presence of various magnetic phases and their nanosized grains. The MFM data of domain size have also been correlated with the observed magnetic behaviour. CoFe/n-Si structures have shown a significant feature of giant magnetoresistance (GMR) as compared to CoFe/p-Si structures. It has been found that CoFe/p-Si structures show a distinctly different behaviour than CoFe/n-Si structures for their chemical structure, morphology and magnetic behaviour.