Abstract In this paper, we focus on the controllable synthesis of BaMnF₄ micro/nanostructures via a facile one-step hydrothermal method assisted by different surfactants. The chemical structure, morphology and superhydrophobic properties have been studied by XRD, SEM, TEM, EDS and CA. The results show that the pH of the starting solution, temperature, reaction time, and surfactant affect the crystallinity, morphology and superhydrophobic properties of the products. The preliminary reaction path and formation mechanisms of the BaMnF₄ with different shapes are also investigated. To the best of our knowledge, the present synthesis route is novel. Furthermore, the as-prepared BaMnF₄ surface shows superhydrophobicity and superoleophilicity.