Provided herein are thermally conductive underfill compositions which have a combination of melt viscosity, glass transition temperature (Tg), coefficient of thermal expansion, and/or transparency that renders such materials useful for the preparation of a variety of electronic devices, such as flip chip packages, stacked dies, hybrid memory cubes, through-silica via (TSV) devices, and the like. In certain embodiments of the invention, there are provided assemblies comprising a first article permanently adhered to a second article by a cured aliquot of a formulation as described herein. In certain embodiments of the invention, there are provided methods for adhesively attaching a first article to a second article. In certain embodiments of the present invention, there are provided methods for improving heat dissipation by electronic devices assembled employing thermally conductive, but electrically non-conductive adhesive.