This paper addresses epitaxial integration of magnetic materials with Si (100) based solid state devices. Epitaxial Ni 82.5 Fe 17.5 (permalloy, Py) thin films have been synthesized by pulsed laser deposition (PLD) on Si (100) using MgO/TiN as a template buffer. This epitaxial growth of these large lattice misfit systems was achieved through domain matching epitaxy (DME). The in-plane XRD pattern and selective area electron diffraction (SAED) results clearly indicate cube-on-cube epitaxial alignment. The bright field TEM image of Py/MgO/TiN/Si (100) heterostructure infers a Py layer thickness of ∼30nm, with a well aligned island (150–200nm) structure that is consistent with Volmer–Weber type growth. Magnetization data collected at 4K and 300K indicates that the easy axis of the magnetization lies in the plane of the Py. In addition, we have observed an intrinsic positive exchange bias (PEB) field of ∼104 Oe, where the magnetic hysteresis loop is shifted toward the positive field axis under zero field cooling conditions.