Harvesting high-purity semiconducting single-walled carbon nanotubes (s-SWCNTs) with removable dispersants remains a challenge. In this work, we demonstrate that small heteroacene derivatives may serve as promising selective dispersants for sorting s-SWCNTs. A rich N “doped” and thiophene-substituted hexaazapentacene molecule, denoted as 4HP, was found to be more favorable for high-purity s-SWCNTs with large diameters. Importantly, 4HP is photodegradable under 365 nm or blue light, which enables a simple deposition approach for the formation of clean s-SWCNT networks. The as-fabricated thin film transistors show excellent performance with a charge-mobility of 30–80 cm² V⁻¹ s⁻¹ and an on–off ratio of 10⁴–10⁶.