The interaction of gaseous AlF with SiO gave Si dendrites and whiskers as a result of the transport chemical reaction of Al, AlF3 and SiO2 starting materials. The reaction yield depends on temperature, transport gas flow-rate, reactor chamber pressure and molar ratio of the initial compounds. The thermodynamic simulation of the processes in reaction chamber was performed by the HSC Chemistry program using HSC-Reaction and HSC-Gibbs modules. Reaction products were characterized by X-ray powder diffraction and scanning electron microscopy. Obtained silicon crystallizes as dendrites and whiskers with diameters ranging from 100 nm to 24 μm. The data obtained demonstrates the potential of the proposed technology for the production of Si anode material. © 2023, The Author(s), under exclusive licence to Springer Nature B.V.