This Study Demonstrated for the First Time an in Situ High-Temperature Fiber-Optic Raman Probe to Study the Structure of Glass and Slag Samples at Temperatures Up to 1400 °C. a Customized External Telescope Was Integrated into a Portable Fiber-Optic Raman Probe to Extend the Optical Working Distance to Allow the Probe to Work in a High-Temperature Environment. Three Samples Were Evaluated to Demonstrate the Functionality of the High-Temperature Fiber-Optic Raman Probe. Room Temperature and High-Temperature Raman Spectra Were Successfully Collected and Analyzed. in Addition, a Deconvolution Algorithm Was Used to Identify Peaks in the Spectrum that Could Then Be Related to the Molecular Structure of Components in Each Sample. This Flexible and Reliable High-Temperature Raman Measurement Method Has Great Potential for Various Applications, Such as Materials Development, Composition, and Structure Monitoring during High-Temperature Processing, Chemical Identification, and Process Monitoring in Industrial Production.