A facile one-pot hydrothermal method was used to synthesize pristine Sb2Te3 and its heterostructure with reduced graphene oxide (rGO). A novel approach dealing with high energy (6 MeV) electron irradiation has been efficiently used for synthesis of gold nanoparticles (Au- NPs) and their in-situ decoration on Sb2Te3-rGO heterostructure. From an application point of view, we have investigated the field electron emission characteristics of pristine Sb2Te3 and Sb2Te3-rGO heterostructures, with and without Au-NPs decoration. The Au-NPs decorated Sb2Te3-rGO heterostructure emitter showed enhanced electron emission behavior in terms of reduced value of turn-on field, delivery of large emission current density (∼1171 µA/cm2) at relatively lower applied field (∼3.1 V/µm), and excellent emission stability. The improvement in emission characteristics upon decoration of Au-NPs is attributed to noticeable increase in the number of emission sites, higher value of field enhancement factor (β = 4562), and betterment in the electronic properties due to Au-NPs-Sb2Te3-rGO interface effects. The obtained results suggest that Au-NPs decorated Sb2Te3-rGO heterostructure emitter has potential towards practical applications in various vacuum microelectronic devices. Furthermore, the present approach dealing with high energy electron irradiation for synthesis and in-situ decoration of nanoparticles can extended to other inorganic heterostructures towards improving their functionality.