Cyberinfrastructure integrates information and communication technologies to enable high-performance, distributed, and collaborative knowledge discovery, and promises to revolutionize the way that science and engineering are conducted in the 21st century. This paper demonstrates the GISolve Toolkit that enhances Geographic Information Systems (GIS) with respect to geospatial problem-solving based on cyberinfrastructure. GISolve is developed as a high-performance, distributed, and collaborative Web GIS powered by cyberinfrastructure capabilities, including high-performance and Grid computing, data management and visualization, and virtual organization support. GISolve architecture is service-oriented that enables interoperable and scalable integration between spatial analysis and basic cyberinfrastructure services. Currently, GISolve is deployed on the National Science Foundation TeraGrid - arguably the most advanced cyberinfrastructure project worldwide. A suite of spatial analyses is employed to demonstrate GISolve functions.