Tissue engineering scaffolds with optimal properties are used as a cell support to favor the regeneration of tissues. Here, we combined the porogen leaching and SC-CO2 assisted solvent removal to prepare polycaprolactone/graphene oxide (PCL-GO) microporous structures. Graphene oxide (GO) was added to PCL structure as a cell interaction platform. Moreover, ethyl lactate (EL) as a green solvent was used in the preparation of scaffolds. Apart from its benign nature, EL enabled us to distribute GO sheets homogeneously in PCL-GO, whereas, use of dichloromethane resulted in agglomeration of GO in PCL-GO structure. Low volatility restriction of EL was overcome by eliminating the solvent in a SC-CO2 assisted process. SEM observations revealed the microporous interconnected structures of the scaffolds. Raman spectra confirmed the presence of GO in PCL scaffolds. PCL-GO scaffolds did not possess any toxicity towards L-929 mouse fibroblasts and cell spreading was triggered in the presence of GO.