Low-field nuclear magnetic resonance (NMR) has three general modalities: spectroscopy, imaging, and relaxometry. In the last twelve years, the modality of spectroscopy, also known as benchtop NMR, compact NMR, or just low-field NMR, has undergone instrumental development due to new permanent magnetic materials and design. As a result, benchtop NMR has emerged as a powerful analytical tool for use in process analytical control (PAC). Nevertheless, the successful application of NMR devices as an analytical tool in several areas is intrinsically linked to its coupling with different chemometric methods. This review focuses on the evolution of benchtop NMR and chemometrics in chemical analysis, including applications in fuels, foods, pharmaceuticals, biochemicals, drugs, metabolomics, and polymers. The review also presents different low-resolution NMR methods for spectrum acquisition and chemometric techniques for calibration, classification, discrimination, data fusion, calibration transfer, multi-block and multi-way.