The work aims to develop ink with both thermal conduction and insulation characteristics to expand the application of ink in electronic devices.Aminated boron nitride (BN-NH2) was synthesized from boron nitride (BN) crystals and urea through ball-milling. With the participation of carboxyl group activator, amidated boron nitride-graphene oxide nanocomposite fillers were prepared through the covalent reaction between the carboxyl group on graphene oxide (GO) and the amino group on BN-NH2. The thermal conductive and insulating ink was developed with the supplement of polymer resins, monomers, pigments and various additives. The morphology, crystal face of BN-NH2 nanosheets and valence bond structure of BN-GO were characterized by means of scanning electron microscope, X-ray diffractometer, laser raman spectrometer, Fourier transform infrared spectrometer and X-ray photoelectron spectrometer. Finally, the printability, thermal conductivity and insulating properties of the ink were tested. The results showed that aminated boron nitride (BN-NH2) and amidated boron nitride-graphene oxide nanocomposite fillers (BN-GO) were successfully synthesized. When the addition amount of BN-GO was 3.0wt.%, the thermal conductive and insulating ink had good printability. After printing and proofing, the thermal conductivity could be increased to 1.45 W/(m∙K), and the volume resistivity could be as high as 9.86×1011Ω.cm, which was 4.8 times and 3.7 times higher than the blank ink samples, respectively. The thermal conductive and insulating ink developed can give the ink excellent thermal conductivity while maintaining good printability.