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Here, we demonstrate that soft organic counter cations, combined with dynamic spiroborate chemistry, enable the rapid synthesis of hydrogen\u2010bonded, single\u2010crystal HCPs, significantly reducing polymerization times compared with analogous systems containing alkali metal cations. Single\u2010crystal X\u2010ray diffraction of HCPs prepared from amines or pyridine with their conjugate acid\n                    <jats:italic>\n                      pK\n                      <jats:sub>a<\/jats:sub>\n                    <\/jats:italic>\n                    values ranging from 4.63 to 10.71 revealed closely related hydrogen\u2010bonded helical backbones associated with nearby organic counter cations. Importantly, counter\u2010cation acidity strongly influences polymerization kinetics and the resulting helical architectures, establishing a previously underexplored strategy for controlling HCP formation. Beyond structural control, these materials exhibit promising solid\u2010state proton\u2010conducting properties, with HCP\u2010TFEA achieving a proton conductivity of 2.8 \u00d7 10\n                    <jats:sup>\u22123<\/jats:sup>\n                    \u00a0S\u00a0cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 70\u00b0C and 97% relative humidity. These findings demonstrate that rational counter\u2010cation selection provides an effective approach to accelerate HCP synthesis while simultaneously tuning polymer structure and function, offering new opportunities for the design of dynamic helical polymeric materials.\n                  <\/jats:p>","DOI":"10.1002\/smll.76153","type":"journal-article","created":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T13:23:46Z","timestamp":1791552226000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Single\u2010Crystal Helical Covalent Polymers with Organic Counter Cations"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-2380-4200","authenticated-orcid":false,"given":"Ashley M.","family":"Ley","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Colorado Boulder  Boulder Colorado USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4075-247X","authenticated-orcid":false,"given":"Hongxuan","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Colorado Boulder  Boulder Colorado USA"},{"name":"State Key Laboratory of Photocatalysis on Energy and Environment, State Key Laboratory of Chemistry for NBC Hazards Protection, College of Chemistry Fuzhou University  Fuzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9515-2602","authenticated-orcid":false,"given":"Simon J.","family":"Teat","sequence":"additional","affiliation":[{"name":"Advanced Light Source Lawrence Berkeley National Laboratory  Berkeley California USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2565-0005","authenticated-orcid":false,"given":"Shaofeng","family":"Huang","sequence":"additional","affiliation":[{"name":"Beckman Institute for Advanced Science and Technology University of Illinois at Urbana\u2010Champaign  Urbana Illinois USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-9511-142X","authenticated-orcid":false,"given":"Zhehao","family":"Yuan","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Colorado Boulder  Boulder Colorado USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5491-1155","authenticated-orcid":false,"given":"Wei","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Colorado Boulder  Boulder Colorado USA"},{"name":"School of Physical Sciences Great Bay University  Dongguan China"},{"name":"Department of Chemistry Kyung Hee University  Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,9]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1038\/171737a0","article-title":"Molecular Structure of Nucleic Acids: A Structure for Deoxyribose Nucleic Acid","volume":"171","author":"Watson J. 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