A hybrid technology that combines a three‐dimensional (3‐D) dispensing system with an electrospinning process was used to produce a hierarchical 3‐D scaffold consisting of micro‐sized polycaprolactone (PCL) strands and micro/nano‐sized fibres. The micro/nanofibre biocomposites electrospun with PCL/small intestine submucosa (SIS) and PCL/Silk fibroin were layered between melt‐plotted micro‐strands. The scaffold containing SIS exhibited a stronger hydrophilic property than other scaffolds due to the various hydrophilic components in SIS. The 3‐D hierarchical scaffold having biocomposites exhibited an incredibly enhanced initial cell attachment and proliferation of bone marrow‐derived mesenchymal stem cells relative to the normally designed 3‐D scaffold.