Combining nanofibers with submicrofibers is an effective way to design morphologically biomimetic tissue engineering scaffolds that imitate natural fibrous extracellular matrix (ECM) with varying lengths from nano‐ to submicrometer scales. Herein, the preparation of ECM‐mimetic scaffolds by conjugating electrospun cellulose acetate (CA) submicrofibers with bacterial cellulose (BC) nanofibers via a facile and scalable dispersion freeze‐drying process is reported. The morphology, structure, mechanical properties, and cell behavior of the as‐prepared nano/submicrofibrous BC/CA scaffolds are assessed. It is found that that the nano/submicrofibrous BC/CA scaffolds have 3D porous network structure with larger pores than the bare BC scaffold. Although the BC/CA scaffolds show decreased mechanical properties and porosity than their BC counterparts, they exhibit improved cell behavior over the bare BC scaffold. Moreover, the submicrofibers enable cell infiltration into the scaffolds. This suggests that the coexistence of nano‐ and submicrometer fibers enhances the attachment and spreading of cells on the nano/submicrofibrous scaffolds. This novel nano/submicrofibrous scaffold has great potential in tissue engineering and regenerative medicine.