Vitrification is considered as an economical and safe treatment technology for low-level radioactive waste (LLW) generated from nuclear power plants (NPPs). Korea is in the process of preparing for its first ever vitrification plant to handle LLW from its NPPs. Polyvinyl chloride (PVC) has the largest volume of dry active wastes and is the main waste stream to treat. Glass formulation development for PVC waste is the focus of study. The minimum additive waste stabilization approach has been utilized in vitrification. It was found that glasses can incorporate a high content of PVC ash (up to 50 wt%), which results in a large volume reduction. A glass frit, KEP-A, was developed to vitrify PVC waste after the optimization of waste loading, melt viscosity, melting temperature, and chemical durability. The KEP-A could satisfactorily vitrify PVC with a waste loading of 30 to 50 wt%. The PVC-frit was tolerant of variations in waste composition.