The data was used when searching for potential biomarkers for southern African hunter-gatherer arrow poisons applied to ethno-historical and archaeological samples using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) and Gas Chromatography Mass Spectrometry (GCMS). All data is presented in a single xlsx-file. The INFO-worksheet contains provenance information of the samples and detailed methods descriptions of the ATR-FTIR and GCMS analyses. The ATR FTIR-data consists of un-normalized absorbance registered at given wavenumbers for each of the samples. The GCMS-data consists of identified components, their retention time and their percent of the total peak area of the total ion-chromatogram of each sample. Unidentified components are marked with a sole “?”.