Chemical and isotopic analyses have been made of pigment samples from two separate rock art sites in Argentina. The purpose of the study has been to establish the feasibility of extracting carbonaceous material from the samples which will permit reliable radiocarbon dates for the time of painting. The two sites, Catamarca and Rio Negro, present quite different problems. Most of the paper is concerned with Catamarca, and here we have shown that the paint pigments contain very little or no organic binder; but they do contain calcium oxalate derived from local cacti, and calcium carbonate derived probably from local plant ash. We describe a method to purify carbon extracted from the calcium oxalate, and present the dates obtained on both components. We show that, though rare, natural deposits containing both calcium oxalate and calcite do occur, but that they are very distinct in both 13C and 14C compositions; and we argue that they are very unlikely to contaminate the pigments to such an extent that the 14C dates are altered. For the Rio Negro site we show that the ground for the paint pigments contains carbon derived from fires burnt inside the cave, and discuss how analytical methods provide information to develop a strategy for extracting material, from both ground and pigment, for more reliable dating.