In-this work, a new procedure for tributyltin (TBT) detection in marine sediments based on cloud point extraction (CPE) followed by total fluorescence spectroscopy combined withmultivariate curve resolution-alternating least squares (MCR-ALS) is proposed. The multivariate model satisfactorily achieved the second order advantage in the presence of uncalibrated interferences, such as butyltin compounds or metallic species that are commonly found in sediment sample extracts. Under optimal conditions, the detection limit reached 3.0 mu g Sn L-1, and the relative prediction error was lower than 10%. The accuracy of the method was validated with the analysis of a certified sediment sample (marine sediment PACS-2), and there was good agreement between the certified and experimental results. Finally, the proposed methodology was satisfactorily applied to spiked real sediment samples, demonstrating the suitability of the proposed method for TBT detection in contaminated sediment samples. (C) 2015 Elsevier B.V. All rights reserved.