This study presents the application of metabolomics to evaluate changes in the rumen metabolites of beef cattle fed with three different diet types: forage-rich, mixed and concentrate-rich. Rumen fluid samples were analysed by 1H-NMR spectroscopy and the resulting spectra were used to characterise and compare metabolomic profiles between diet types and assess the potential for NMR metabolite signals to be used as proxies of methane emissions (CH 4 in g/kg DMI). The dataset available consisted of 128 measurements taken from 4 experiments with CH 4 measurements taken in respiration chambers. Predictive modelling of CH 4 was conducted by partial least squares (PLS) regression, fitting calibration models either using metabolite signals only as ...