The methods of linear and rank correlation and normalized coordinates (MNC) have been applied to the identification of organic solid materials with a very similar chemical composition by laser-induced breakdown spectroscopy (LIBS). The present study evaluated these three statistical methods using an Echelle spectrometer coupled with an intensified charge-coupled device (ICCD). Moreover, three instrumental parameters (laser pulse energy, delay time and integration time) were evaluated in terms of their influence on the signal-to-noise ratio of carbon and hydrogen emission lines. The probability of a right identification can be estimated by means the described methods in this paper. Methods of correlation provide better identification and discrimination than normalized coordinates at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.