Microstructural characterisation of engineering materials is required for understanding the relationships between microstructure and mechanical properties. Conventionally grain size is measured from grain boundary maps obtained using optical or electron microscopy. This paper implements EBSD-based linear intercept measurement of spatial grain size variation for ferritic steel weld metals, making analysis flexible and robust. While grain size has been shown to correlate with the strength of the material according to the Hall–Petch relationship, similar grain sizes in weld metals with different phase volume fractions can have significantly different mechanical properties. Furthermore, the solidification of the weld pool induces the formation of grain sub-structures that can alter mechanical properties. The recently developed domain misorientation approach is used in this study to provide a more comprehensive characterisation of the grain sub-structures for ferritic steel weld metals. The studied weld metals consist of varying mixtures of primary ferrite, acicular ferrite, and bainite/martensite, with large differences observed in hardness, grain size, grain morphology, and dislocation cell size. For the studied weld metals, the average dislocation cell size varied between 0.68 and 1.41 µm, with bainitic/martensitic weld metals showing the smallest sub-structures and primary ferrite the largest. In contrast, the volume-weighted average grain size was largest for the bainitic/martensitic weld metal. Results indicate that a Hall–Petch-type relationship exists between hardness and average dislocation cell size and that it partially corrects the significantly different grain size—hardness relationship observed for ferritic and bainitic/martensitic weld metals. The methods and datasets are provided as open access.