Guided bone regeneration (GBR) is an extensively used technique for the treatment of maxillofacial bone defects and bone mass deficiency in clinical practice. However, to date, studies on membranes for GBR have not achieved the combination of suitable properties and cost-effective membrane production. Herein, we developed a polycaprolactone/human extracellular matrix-like collagen (PCL/hCol) membrane with an asymmetric porous structure via the nonsolvent-induced phase separation (NIPS) method, which is a highly efficient procedure with simple operation, scalable fabrication and low cost. This membrane possessed a porous rough surface, which is conducive to cell attachment and proliferation for guiding osteogenesis, together with a relatively smooth surface with micropores, which allows the passage of nutrients and is unfavorable for the adhesion of cells, thus preventing fibroblast invasion and overall meeting the demands for GBR. Besides, we evaluated the characteristics and biological properties of the membrane and compared them with those of commercially available membranes. Results showed that the PCL/hCol membrane exhibited excellent mechanical properties, degradation characteristics, barrier function, biocompatibility and osteoinductive potential. Furthermore, our in vivo study demonstrated the promotive effect of the PCL/hCol membrane on bone formation in rat calvarial defects. Taken together, our NIPS-prepared PCL/hCol membrane with promising properties and production advantages offers a new perspective for its development and potential use in GBR application.