Due to the much lower production costs but similar effects to lysergic acid diethylamide (LSD), phenethylamine derivatives are sold as a cheaper replacement or deceptively as LSD itself. These potent hallucinogenic substances can lead to severe intoxication, thus a more profound understanding of their use is required. This includes the elucidation of the manufacturing processes for the commonly used blotter papers and the assessment of the risk of overdosing because of a heterogeneous distribution on the blotter papers. Besides the rapid detection of the analytes, the manufacturing process was elucidated by three different imaging techniques and liquid chromatography‐mass spectrometry (LC–MS). A blotter paper sample, containing the two hallucinogenic phenethylamine derivatives 25I‐NBOMe and 25C‐NBOMe, was analyzed by complementary techniques such as micro x‐ray fluorescence (μXRF), laser ablation (LA)‐inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), matrix assisted laser desorption ionization (MALDI)‐MS, and with LC–MS after extraction. Using the signal from chlorine and iodine within the compounds, μXRF proved to be the fastest, cheapest and easiest method for identification, requiring no sample preparation at all. LA‐ICP‐OES provided three‐dimensional information of the elements in the blotter paper. These results helped to confirm the assumption that manufacturers spray the compounds onto the paper. Whereas μXRF and LA‐ICP‐OES detected signals for chlorine and iodine, MALDI‐MS‐imaging showed the molecular distribution of both analytes. LC–MS analyses as a complementary method support the imaging results. Quantitative results for different drug hotspots revealed a heterogeneous distribution of the drugs on the blotter paper implying an inherent risk of overdosing for consumers.