NMR spectroscopy is an established powerful tool for reaction monitoring, but there are associated challenges with using it as a PAT tool. Nonetheless, it is an attractive method for calibrating optical techniques such as FTIR and Raman due to its inherent quantitative nature. It is also a complimentary and orthogonal analytical tool that strengthens the fusion of data, providing robust analysis of reaction processes. However, the requirement of manual sampling followed by offline analysis can be laborious and time-consuming, particularly for lengthy reactions. To overcome these challenges, here we report an innovative approach to couple benchtop NMR with a probe-based autosampler to enable the automatic sampling and online measurement of the reaction samples as well as the verification and calibration of the inline FTIR trends.