Vertical aligned carbon nanotube (VACNT) arrays used as dry adhesive materials have broad prospects in the applied fields of space, medicine and electronics. The adhesion of VACNT arrays is believed to be related not only to the nano-array structure and a clean surface, but also to chemical composition. Here, radio-frequency (RF) carbon dioxide (CO2) plasma treatment is introduced as an effective method for purifying and functionalizing the surface to improve the dry adhesive performance of VACNT arrays. Scanning electron microscopy showed that the VACNT arrays retained the alignment architecture with minimal damage at low power. X-ray photoelectron spectroscopy and contact angle tests revealed that the content of non-polar components (C = C bonds) decreased after treatment, while the content of polar groups (C = O and O-C = O bonds) increased, which changed the surface polarity of the VACNT arrays. Raman analyses and transmission electron microscopy demonstrated that amorphous carbon can be selectively removed with increasing time (0-18 min), but was continuously generated with increasing power (30-90 W). The best adhesive strength of 18 N cm-2 (increased by 39%) was obtained after CO2 plasma treating for 10 min at 30 W power, which was attributed to the combined action of purification and polarization.