This work reports on the quantitative determination of the carboxylic groups created upon HNO3 treatment at multi-wall carbon nanotube (MWCNT) surface. To this purpose, MWCNTs have been oxidized by refluxing in acid for different periods of time (from 1 h to 12 h). The main goal of the present study comprises the development of a simple analytical methodology based on Boehm's titration that enables the rapid estimation of the total carboxylic groups and their discrimination from the total oxidized sites created at MWCNT surface as a result of the acid treatment. The trends observed are correlated with Raman spectroscopy analyses. © 2008 Elsevier B.V. All rights reserved.