To better engineer small-diameter blood vessels, a few types of novel scaffolds are fabricated from biodegradable poly(L-lactic acid) (PLLA) by means of thermally induced phase-separation (TIPS) techniques. By utilizing the differences in thermal conductivities of the mold materials and using benzene as the solvent scaffolds with oriented gradient microtubular structures in the axial or radial direction can be created. The porosity, tubular size, and the orientational direction of the microtubules can be controlled by the polymer concentration, the TIPS temperature, and by utilizing materials of different thermal conductivities. These gradient microtubular structures facilitate cell seeding and mass transfer for cell growth and function. Nanofibrous scaffolds with an oriented and interconnected microtubular pore network are also developed by a one-step TIPS method using a benzene/tetrahydrofuran mixture as the solvent without the need for porogen materials. The structural features of such scaffolds can be conveniently adjusted by varying the solvent ratio, phase-separation temperature, and polymer concentration to mimic the nanofibrous features of an extracellular matrix. These scaffolds were fabricated for the tissue engineering of small-diameter blood vessels by utilizing their advantageous structural features to facilitate blood-vessel regeneration.