The matrix structure formation of cast irons is strongly affected by the casting process where different alloying elements and cooling conditions are methods used to achieve the desired structure and performance of the material. In the presented study, six pearlitic grey cast irons have been analysed regarding how the pearlitic structure formation might be controlled. Different amounts of copper and chromium were added, ranging from 0.07 to 1.11 wt% and 0.08 to 0.60 wt%, respectively. Three different section sizes (Ø20, Ø45 and Ø85 mm) and three different cooling conditions through the eutectoid transformation were used to control the matrix structure formation. The three different cooling conditions were achieved by shake-out at 950°C and cooling in air or furnace, or by keeping the casting in the mould. The present paper focuses on the pearlite appearance, since it strongly affects the mechanical properties. The analysis shows that the refining effect of Cr is much stronger than that of Cu. Comparing the low alloyed base melt with the ones alloyed with Cu and Cr, it is seen that additions of 0.75 wt% Cu refines the pearlite by approximately 10%. Keeping this Cu level constant and adding Cr, it is observed that an addition of ~0.6 wt% refines the pearlite by another 20%. The most potent refining effect of Cr is achieved by additions up to 0.35 wt%. Keeping the Cr constant at 0.35% and changing the Cu content (0.35 to 1.10 wt%), almost no variation is observed in the overall interlamellar spacing. The eutectoid cooling rate most strongly affects the interlamellar spacing down to cooling rates of about -0.75 °C/s. At higher (i.e. lower value) cooling rates the interlamellar spacing is fairly constant. In addition to studying the interlamellar spacing, the graphite structure has also been analysed and evaluated concerning effects from the different casting variables.