Novel tri‐layered electrospun alginate–graphene oxide (GO)/poly(ε‐caprolactone) (PCL) conductive scaffolds were fabricated with a sequential electrospinning method for the first time, in which the middle PCL layer acts as a mechanical support of the scaffold. The top and bottom alginate–GO nanofibrous layers provide cell viability and attachment, and also electroconductivity for the scaffold. The fabrication of this nanofibrous scaffold aims to simulate cardiac extracellular matrix. Scanning electron microscopy and infrared spectroscopy were used to characterize the nanofibrous scaffolds, confirming the presence of GO in nanofibers and also crosslinking reaction of the alginate nanofibrous layer. The electroconductivity of the tri‐layered electrospun scaffolds reached 7.29 ± 0.91 μS with the incorporation of 1 wt% GO into the top and bottom alginate nanofibrous layers. The ultimate tensile strength and Young’s modulus of the alginate–0.5 wt% GO/PCL scaffold reached 22.46 ± 0.07 and 4.35 ± 0.56 MPa, respectively. The biocompatibility of the nanofibrous scaffolds was evaluated using cardiac progenitor cells. The results showed that the presence of GO accelerated the degradation of the scaffolds in phosphate‐buffered saline solution. The cell studies revealed that GO incorporation into alginate nanofibers on the surface of the tri‐layer scaffolds could enhance cell viability, adhesion and proliferation. Overall, the tri‐layered electroconductive alginate–PCL nanofibrous scaffolds could be considered as potential candidates for cardiac tissue regeneration. © 2022 Society of Industrial Chemistry.