Long-term decarbonisation pathways to achieve ambitious low-carbon targets involve a range of uncertainties. Different energy system modelling approaches can be used to systematically evaluate the influence of the uncertainties, but this often leads to an unmanageable number of pathways. Summarising the large ensemble through a more limited number of representative pathways, to inform stakeholders, can be challenging. This study thus explores how to identify representative decarbonisation pathways using clustering algorithms, which can assist in grouping similar data points in uncategorised datasets, such as pathway ensembles. However, the suitability of clustering algorithms for pathway characterisation has not been investigated to date. Hence, k-means, hierarchical clustering, Gaussian mixture model, spectral clustering, and density-based clustering are adopted for comparisons. An illustrative pathway ensemble for the United Kingdom is applied to evaluate their performance based on cluster validity indices. Three metric transformations, including power, standardisation and sectoral standardisation, are also applied to create three additional sets of pathways for testing. The k-means algorithm is found to outperform others consistently, although hierarchical clustering might also be applicable if the distribution of pathway proximity is uneven. The results also highlight the utility of the approach in revealing distinctive trade-offs between technologies among the identified representative pathways. For instance, the electrification of heating can be replaced by district heating in the residential sector. The described, novel approach can be applied to characterise other sets of pathways, with greater technological details generated by any energy system models, to reveal insights for long-term decarbonisation.