Helical　morphologies　are　widely　observed　in　nature,　however,　it　is　very　challenging　to　prepare　artificial　helical　polymers.　Especially,　precisely　understanding　the　structure　information　of　artificial　metal-free　helical　covalent　inorganic　polymers　via　single-crystal　X-ray　diffraction　(SCXRD)　analysis　is　rarely　explored.　Here,　we　successfully　prepare　a　novel　metal-free　helical　covalent　inorganic　polymer　({[Te(C6H5)2]　[PO3(OH)]}n,　named　CityU-10)　by　introducing　angular　anions　(HOPO32−)　into　traditional　tellurium-oxygen　chains.　The　dynamic　reversibility　of　the　reaction　is　realized　through　the　introduction　of　organic　tellurium　precursor　and　the　slow　hydrolysis　of　polyphosphoric　acid.　High-quality　and　large-size　single　crystals　of　CityU-10　have　been　successfully　characterized　via　SCXRD,　where　the　same-handed　helical　inorganic　polymer　chains　form　a　pseudo-two-dimensional　layer　via　multiple　hydrogen-bonding　interactions.　The　left-handed　layers　and　right-handed　layers　alternatively　stack　together　through　weak　hydrogen　bonds　to　form　a　three-dimensional　supramolecular　structure.　The　single　crystals　of　CityU-10　are　found　to　display　promising　optical　properties　with　a　large　birefringence.　Our　results　would　offer　new　guidelines　for　designing　and　preparing　new　crystalline　covalent　polymers　through　tellurium-based　chemistry.　©　2023　Wiley-VCH　GmbH.