Poly(L-lactic acid) (PLLA) tissue engineering scaffolds with porous inner structures of individual fibers and controllable architectures were successfully fabricated from the homogeneous polymer-solvent-nonsolvent system (PLLA, CH(2)Cl(2) and DMF) by a single capillary electrospinning with certain conductive patterned templates as fiber collectors. PLLA was dissolved in dimethylformamide (DMF) and methylene chloride (CH(2)Cl(2)) mixed solvent with different ratios. Semi-hollow fiber with porous inner structure and compact shell wall was formed by controlling the content of DMF in the mixed solvents. It is believed that the phase separation should be the key origin for the formation of this microstructure. In order to mimic the natural extracellular matrix (ECM) with a specific structure, conductive patterned collectors were designed and employed to manufacture PLLA ultrafine fibrous scaffolds with three-dimensional architectures. We believe these kinds of multi-scale biodegradable fibrous scaffolds with specific microstructure and macro-architectures could make the electrospun fibrous scaffold better mimic the natural extracellular matrix to satisfy tissue engineering.