In this work, an easy, reliable, effective approach for preparation of modified Boron Nitride (BN) from h-BN(Hexagonal boron nitride) was developed via liquid-phase exfoliation using a dopamine chemistry. Supramolecular interactions of the polydopamine (PDA) with h-BN has been used to achieve the facile surface modification of h-BN by forming a PDA shell on its surface. The successful and effective preparation of different h-BN-PDA hybrids has been confirmed by Scanning Electron Microscopy (SEM), Raman spectroscopy, XRD, IR and TGA investigations. The PDA coating increases the dispersibility of these hybrids as filler in polymers. Since polymer-based thermal interface materials (TIMs) with excellent thermal conductivity and electrical resistivity are in high demand, epoxy composites filled with h-BN, BBN (Ball milled Boron Nitride), MBN (Modified Boron Nitride) and MBBN (Modified Ball milled Boron Nitride) were processed. The thermal conductivity is as high as 4 W/mK for MBBN as compared with 0.2 W/mK of neat epoxy. This method of producing multifunctional exfoliated h-BN provides eco-friendly, easy handling, and suitable as a unique paradigm for developing the next generation of thermal conductive devices and solution-processed semiconductors.