A new family of materials that synergistically combine the attributes of both organic and inorganic properties for use in organic light emitting diodes (OLEDs) is presented. The hybrid materials are based on 3-D inorganic cores of octavinylsilsesquioxanes (OVS). The resultant materials have high Tg's (120–210°C), are formed from minimal step/high yield reactions and readily available starting reagents, are monodisperse (PDI<1.1), can be highly purified via common chroma-tographic techniques, and form defect-free amorphous films via spin-dip coating. For example TPD is known for its good hole injection/transport properties in OLED applications but suffers from a low Tg (65°C). TPD-OVS hybrid material has a Tg of 142°C while maintaining similar injection/transport properties to TPD. Photoluminescence analysis of the hybrid thin film reveals: 1) a 30 nm blue shift versus their dilute solution counterparts; and 2) 5 hour annealing cycles to within 10°C of their Tg show no indication of eximer formation (no red shift) that often causes reduced efficiencies in polymer LEDs.