Tungsten　coatings　have　unique　properties　such　as　high　melting　points　and　hardness　and　are　widely　used　in　the　nuclear　fusion　and　aviation　fields.　In　experiments,　compared　to　pure　Na2WO4　molten　salt,　electrolysis　with　Na2WO4-WO3　molten　salt　results　in　a　lower　deposition　voltage.　Herein,　an　investigation　combining　experimental　and　computational　approaches　was　conducted,　involving　molecular　dynamics　simulations　with　deep　learning,　high-temperature　in　situ　Raman　spectroscopy　and　activation　strain　model　analysis.　The　results　indicated　that　the　molten　salt　system＇s　behaviour,　influenced　by　migration　and　polarization　effects,　led　to　increased　formation　of　Na2W2O7　in　the　Na2WO4-WO3　molten　salt,　which　has　a　lower　decomposition　voltage　and　subsequently　accelerated　the　cathodic　deposition　of　tungsten.　We　analyzed　the　mechanism　of　the　effect　of　the　electric　field　on　the　Na2W2O7　structure　based　on　the　bond　strength　and　electron　density.　This　research　provides　crucial　theoretical　support　for　the　effect　of　electric　field　on　tungsten　in　molten　salt　and　demonstrates　the　feasibility　of　using　machine　learning-based　DPMD　methods　in　simulating　tungsten-containing　molten　salt　systems.　©　2024　The　Royal　Society　of　Chemistry.