With the ultra-fast development of personal portable electronic devices, it is important to explore new die attach film (DAF) materials in the limited mounting area and height in order to meet the requirements of a high packaging density and a high operating speed. Graphene-based epoxy nanocomposites are becoming one of the most promising candidates for the next generation of DAFs combining the ultra-high thermal conductivity of graphene, and ultra-strong adhesion of epoxy polymers. However, poor dispersion and weak interfacial connections, due to the overly smooth surface of graphene nanosheets, are still pressing issues that limit their industrial applications. Additionally, pristine graphene nanosheets have only a small effect on improving the glass transition temperature (Tg) of epoxy composites to meet the requirements of DAFs. In this work, melamine-functionalized graphene is synthesized by using a nondestructive ball milling process, which results in greater dispersion and enhancement of the interfacial connections between graphene and epoxy resins demonstrated by both experimental and simulation results. In particular, the aromatic triazine rings of melamine increase Tg in the cured resin, thus improving the thermal stability of DAFs. The melamine-graphene (M-G) epoxy nanocomposites synthesized have a high Tg of 172 °C and an out-of-plane thermal conductivity of 1.08 W m-1 K-1 at 10 wt% loading. This is 6.4 multiples higher than that of neat epoxy. Moreover, M-G epoxy nanocomposites exhibit superb thermal stability, an effective low coefficient of thermal expansion (CTE), low moisture adsorption, and a useful high electrical resistivity. In the DAF performance test, involving experimentation and modeling, the samples present a better cooling capability and heat dissipation. This supports the idea that our findings have potential to be applied in the next generation of DAFs for high-power and high-density 3D packaging.