In this paper, a robust method based on solvent-volume controlled full evaporation headspace gas chromatography technique (FE HS-GC) was developed to high throughput quantify gamma-valerolactone (GVL) concentration in sample solution. The results showed that the full evaporation of GVL can be achieved by the equilibration process in headspace sampler at 150 degrees C for 5 min. For eliminating the matrix effect and pressure effect on GVL quantification, the sample volume added in headspace vial should be controlled within 15 mu L. The present method was proved that has a very high precision (error < 1.11%), high precision (recoveries from 95.6% to 102.1%), and an excellent limit of quantification (153 mg/L). The present method was applied in valuation of GVL yield in a heterogeneous catalytic system and its recovery in a GVL-based biomass pretreatment process, and has given some valuable information. The present method is simple, rapid, efficient, and can be an excellent tool for screening reaction medium and catalysts in GVL synthesis and its related biorefinery processes.