The effect of cooling rate on the interlaminar fracture toughness of Carbon reinforced PPS laminates was investigated experimentally. A typical stamp forming process was utilised in a novel manner to achieve high average cooling rates, of up to 3500 °C/min, while ensuring a good consolidation quality. Differential scanning calorimetry measurements were used to characterise the degree of crystallinity of the samples, while the interlaminar fracture toughness of the laminates was characterised under mode I using the Double Cantilever Beam test. Finally, micrographic analysis of the fracture surfaces was carried out to correlate the degree of crystallinity to the failure modes. A strong correlation between fracture toughness and degree of crystallinity was found. The samples with a low degree of crystallinity showed a high interlaminar fracture toughness and large plastic deformation of the matrix during fracture.