Smoking pipes discovered in archaeological contexts demonstrate that Indigenous peoples of the Pacific Northwest of North America have practiced smoking for over 4,500 years. Archaeometry and ancient residue metabolomics provide evidence for the association of particular plants with these artifacts. In this article, we synthesize recent research on ancient smoking and present current knowledge on the spatiotemporal distribution of smoking in the past. The presence of stone smoking pipes in the archaeological record is paired with our understanding of past plant use based on chemical residue analyses to create a picture of precontact smoking practices. Archaeological pipe data demonstrate that smoking was a widely distributed practice in the inland Northwest over the past several thousand years, but not on the coast. Distributional data—including positive and negative evidence from chemical residue studies—show that tobacco was an important smoke plant in the region as early as around 1,410 years ago and as far north as the mid-Columbia region. Ancient residue metabolomics contributes to a richer understanding of past use of specific plants through the identification of tobacco species and other indigenous plants, including Rhus glabra, Cornus sericia, and Salvia sp., as contributing to the chemical residues in ancient pipes.