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An overview of representative studies on rock art paintings applying physicochemical techniques to investigate their composition is presented. Advantages and limitations of the different techniques, protocols and recommendations for sampling and proposals to deal with difficulties are discussed. Portable instrumentation and non-destructive multi-technique methodology are highly advisable. Contamination and the presence of non-pictorial materials must always be taken into account because rock art is an open-air scenario. Accretions, alterations, deterioration and possible remedies are considered. The results obtained are very useful for archaeologists and conservators. The use of new techniques and instrumentation augurs a promising future in this field.

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