In this study, we employ wavelength‐dispersive X‐ray fluorescence (WDXRF) to characterize construction materials from Formative civic architecture (1000 B.C.E.–C.E. 400), ethnographic mudbricks, and off‐site controls from the Taraco Peninsula, Bolivia. The preparation of earthen construction materials for civic buildings can shed light on aspects of community development such as labor organization, resource management, and architectural technologies. We apply geochemical results to reconstructing how public buildings were made as communities moved toward socio‐political complexity in this region. However, there are few geochemical studies in the Andes, and little prior scientific analysis of earthen architecture. We therefore tested the efficacy of WDXRF for this region, and developed control materials. Our archaeological samples were selected from two Formative villages, Chiripa and Kala Uyuni. In this study, we performed WDXRF analyses on 63 archaeological and control samples including archaeological floors, walling, plasters, and mortars, as well as contemporary ethnographic walling and topsoils. Elemental signatures for 28 elements clearly distinguished the archaeological flooring, walling, plaster, and mortars from ethnographic and off‐site controls. More subtle variations were detected that distinguish study sites and the different material types. Laboratory‐calibrated multi‐element XRF effectively supports efforts to reconstruct the pathways to social complexity in the Titicaca Basin.