In the present study, we investigated by the joint use of portable instrumentations, namely a handheld X-ray fluorescence (XRF) analyser and a portable Raman spectrometer, the painted surface of plasters withdrawn from different areas of an important Roman monumental complex, known as Villa dei Quintili (Rome, Italy), dated back to the first half of the 2nd century a.C. XRF and Raman measurements contributed to the identification of the pigments through the elemental and molecular composition, respectively. In particular, the multi-technique non-invasive approach proved to be crucial for distinguishing two different reddish pigments. In order to confirm and integrate XRF and Raman results, two micro-destructive laboratory methods, namely optical microscopy (OM) and scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDS), were also employed on the same samples. All the experimental results shed light on the material characterizing the painted surface layer and the painting methodologies, providing in principle useful information for proper restoration processes. It is worth underlining that this experimental investigation takes part of a recent multidisciplinary study performed on this impressive archaeological site, aimed to characterize for the first time the monumental complex from an archaeometric point of view. (C) 2015 Elsevier B.V. All rights reserved.