Semiconducting single‐walled carbon nanotube (CNT) is a promising candidate as a channel material for advanced logic transistors, attributed to the ultra‐thin 1‐nm cylindrical geometry, high mobility, and high carrier injection velocity. However, the presence of undesired CNT bundles in the CNT arrays for wafer‐scale device fabrication, even when utilizing the state‐of‐the‐art dimension‐limited self‐alignment (DLSA) method, poses challenges. These CNT bundles degrade the transistor gate's efficiency in controlling the flow of charge carriers in the CNT channel, leading to pronounced device‐to‐device variability. Here, a novel method is introduced to alleviate bundling in CNT arrays assembled via DLSA, by involving small molecule additive to screen the attractive van der Waals force between neighboring CNTs during the DLSA process, resulting in over 50% reduction in CNT bundling. Furthermore, a pioneering methodology for quantifying CNT bundles is presented and employed experimentally to assess bundles in dense CNT arrays assembled by DLSA using transmission electron microscopy. Both experimental data and molecular dynamics simulation reveal that CNT bundling originates from van der Waals attraction between CNTs, and the disturbed liquid‐liquid interface by accumulating excess polar molecules. These findings illuminate new pathways for realizing dense, bundle‐free CNT arrays. Single‐walled carbon nanotubes (CNTs) offer great potential for advanced transistors. Yet, undesired CNT bundles pose challenges. This method reduces 50% of bundling by using small molecule additives to screen van der Waals attraction during assembly. The degree of CNT bundles is quantified by transmission electron microscopy. Experiment and simulation reveal that bundling originates from inter‐tube attraction and mixed liquid‐liquid interface.