The morphology changes in graphite flakes due to the difference in S and Mn contents were analyzed in gray iron samples with a Carbon Equivalent (CE) of 4.0. Although these Mn and S contents are within the range of industrial usage, the morphological characteristics of graphite flakes among the different samples show significant changes in their size and distribution. Graphite flake size was estimated using the Feret diameter, and the flake’s distribution was visually characterized following established standards. As it was observed that graphite flakes also differ in branching, a new procedure was developed to quantify such branching. Based on a skeletonization technique, this new procedure provides data to obtain additional microstructural parameters of the graphite flakes, such as the percentage of branched flakes and the longest shortest path (LSP) of each graphite flake. Microstructural characterization included measuring the eutectic cell count. The results indicate that Feret values and LSP show only weak correlations with concentration estimates from initial S and Mn. The most notable relationships are between sulfur content and Feret or LSP values. In contrast, the branching percentage correlates well with free sulfur at 1150 °C and eutectic cell count and is also linked to graphite distribution types (A or B). Notably, branching percentage offers a straightforward morphological parameter that enhances graphite flake characterization.