Well-aligned carbon nanotubes (CNTs) with large diameters (25-200 nm) were synthesized by pyrolysis of iron(II) phthalocyanine. The outer diameter up to 218.5 nm and the length of the well-aligned CNTs can be systematically controlled by varying the growth time. A tube-in-tube nano-structure with large and small diameters of 176 and 16.7 nm, respectively, was found. The grain sizes of the iron catalyst play an important role in controlling the CNT diameters. These results are of great importance to design new aligned CNT-based electron field emitters in the potential application of panel displays.