We investigate the role of precursor thermal rearrangement and surface catalytic reactions in the synthesis of vertically aligned carbon nanotubes (VA-CNTs) by acetylene-based, chemical vapor deposition (CVD) and demonstrate a millimeter-long growth of single-walled CNT (SWNT) without water assistance. A substrate heater was used to create an ascending temperature gradient from gas injection to catalyst substrate. Whereas temperature of catalyst substrates primarily determines their catalytic activity, it is a thermal condition of a gaseous mixture in the CVD chamber that also influence growth yield and structural features of as-grown CNTs. Employing Egloff’s characterization, [1] we discuss the importance of various gas thermal zones in producing high-quality nanotubes with augmented growth efficiency. We continue to report production of millimeter-long, VA-SWNT having a mean diameter of 1.7 ± 0.7 nm, catalyzed by iron on an alumina support. Important finding is that a million of aspect ratio of SWNT arrays can be produced, without water assistance, via combined action of an ascending temperature gradient toward catalyst substrate and low partial pressures of acetylene carbon feedstock. Our results do not only emphasize the role of precursor thermal rearrangement in CNT synthesis, but also offer a practical route to the modulation of such complex phenomena for an ultrahigh-yield growth of narrow VA-SWNT.