Geology and hydrology are drivers of water chemistry and thus important considerations for fish otolith chemistry research. However, other factors such as species and habitat identity may have predictive ability, enabling selection of appropriate elemental signatures prior to costly, perhaps unnecessary water/age‐0 fish sampling. The goal of this study was to develop a predictive methodology for using species and habitat identity to design efficient otolith chemistry studies. Duplicate water samples and age‐0 fish were collected from 61 sites in 4 Missouri River reservoirs for walleye Sander vitreus and one impoundment (Lake Sharpe, South Dakota) for other fishes (bluegill Lepomis macrochirus, black crappie Pomoxis nigromaculatus, gizzard shad Dorosoma cepedianum, largemouth bass Micropterus salmoides, smallmouth bass M. dolomieu, white bass Morone chrysops, white crappie P. annularis, and yellow perch Perca flavescens). Water chemistry (barium:calcium [Ba:Ca], strontium:calcium [Sr:Ca]) was temporally stable, spatially variable, and highly correlated with otolith chemistry for all species except yellow perch. Classification accuracies based on bivariate Ba:Ca and Sr:Ca signatures were high (84% across species) yet varied between floodplain and main‐channel habitats in a species‐specific manner. Thus, to maximize the reliability of otolith chemistry, researchers can use species classifications presented herein to inform habitat selection (e.g., study reservoir‐oriented species such as white bass in main‐channel environments) and habitat‐based classifications to inform species selection (e.g., focus floodplain studies on littoral species such as largemouth bass). Overall, species and habitat identity are important considerations for efficient, effective otolith chemistry studies that inform and advance fisheries and aquatic resource management.