Plain carbon steels of five different carbon contents up to eutectoid composition have been provided with the conventional full annealing treatment. Qualitative and quantitative studies of the microstructure are carried out using optical microscopy and field emission scanning electron microscopy techniques. Even under similar cooling rate pertaining to the full annealing treatment (furnace cooling); microstructural modifications of individual microconstituents are feasible with varying chemistry (carbon content) of plain carbon steel. The refinement of microstructure for both proeutectoid α‐ferrite and pearlite is found to be accentuated with increasing carbon content of annealed steels till eutectoid composition. Hall‐Petch type relationship explains adequately the relationship between hardness and the size of the microconstituent both in terms of the grain size of proeutectoid α‐ferrite and the interlamellar spacing of pearlite. Henceforth an empirical relationship is developed for the first time taking into account the rule of mixture to correlate overall hardness, carbon content, grain size of proeutectoid α‐ferrite and interlamellar spacing of pearlite. The empirical relationship originated thereby is found to closely match the experimental results.