AbstractDichlorocarbene is added to the sidewalls of single‐walled carbon nanotubes (SWNTs) with diameters ranging from 1.2 to 2.2 nm. Small diameter SWNTs are found to react much more easily than large diameter SWNTs. Upon functionalization, the conductance could be largely preserved for almost all SWNTs, while an effective bandgap increase for functionalized metallic SWNTs (m‐SWNTs) and a bandgap reduction for functionalized semiconducting SWNTs (s‐SWNTs) are generally observed. The results suggest that [2 + 1] cycloaddition is an excellent choice of processing, resulting in SWNTs over a large diameter range with electronic properties that are almost unaffected. Furthermore, possible separation of SWNTs according to their diameters could be achieved due to the apparent diameter‐dependent reactivity.