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Biodegradable scaffolds of poly (L-lactide-co-ε-caprolactone) (PLCL) and reduced graphene oxide (rGO) were prepared by TIPS (thermally induced phase separation). The nonisothermal cold crystallization kinetics were investigated by differential scanning calorimetry (DSC) with various cooling rates. The experimental values indicate that nonisothermal crystallization improves with cooling rate, but the increasing rGO concentration delays crystallization at higher temperatures. The activation energies were calculated by the Kissinger equation; the values were very similar for PLCL and for its compounds with rGO. The electrical conductivity measurements show that the addition of rGO leads to a rapid transition from insulating to conductive scaffolds with a percolation value of ≈0.4 <i>w</i>/<i>w</i>. Mechanical compression tests show that the addition of rGO improves the mechanical properties of porous substrates. In addition, it is an anisotropic material, especially at compositions of 1% <i>w</i>/<i>w</i> of rGO. All of the samples with different rGO content up to 1% are cytotoxic for C2C12 myoblast cells.