Acquiring metal-free horizontal single-walled carbon nanotube (SWNT) arrays is of paramount importance for the development of stable nanodevices. However, the majority of SWNTs are prepared with transition metal-based catalysts, which will inevitably leave metallic residuals and deteriorate the device performance. Here, green and low-cost NaCl is developed as a metal-free catalyst. By employing a strategy of rapid nucleation at a higher temperature followed by steady growth at a lower temperature, the production of a well-defined NaCl catalyst capable of growing metal-free horizontal SWNT arrays with an average density of ∼100 tubes per 100 μm is realized. Besides, we prove that the as-grown metal-free SWNT arrays have a unique advantage in preparing stable devices for eliminating the potential risk of local mass catalyst residuals. Hence, the current study can offer a feasible solution to promote practical applications of SWNT-based next-generation nanodevices.