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Here, the electrochemistry at the one\u2010dimensional (1D) edge of a graphene sheet, sandwiched between two hexagonal boron nitride (hBN) flakes, is reported. When such an hBN\/graphene\/hBN heterostructure is immersed in a solution, the basal plane of graphene is encapsulated by hBN, and the graphene edge is exclusively available in the solution. This forms an electrochemical nanoelectrode, enabling the investigation of electron transfer using several redox probes, e.g., ferrocene(di)methanol, hexaammineruthenium, methylene blue, dopamine and ferrocyanide. The low capacitance of the van der Waals edge electrode facilitates cyclic voltammetry at very high scan rates (up to 1000\u00a0V\u00a0s\n                    <jats:sup>\u22121<\/jats:sup>\n                    ), allowing voltammetric detection of redox species down to micromolar concentrations with sub\u2010second time resolution. The nanoband nature of the edge electrode allows operation in water without added electrolyte. Finally, two adjacent edge electrodes are realized in a redox\u2010cycling format. All the above\u2010mentioned phenomena can be investigated at the edge, demonstrating that nanoscale electrochemistry is a new application avenue for van der Waals heterostructures. Such an edge electrode will be useful for studying electron transfer mechanisms and the detection of analyte species in ultralow sample volumes.\n                  <\/jats:p>","DOI":"10.1002\/smll.202306361","type":"journal-article","created":{"date-parts":[[2023,12,18]],"date-time":"2023-12-18T11:35:05Z","timestamp":1702899305000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Electrochemistry at the Edge of a van der Waals Heterostructure"],"prefix":"10.1002","volume":"20","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4863-8666","authenticated-orcid":false,"given":"Aleksandra","family":"Pla\u010dki\u0107","sequence":"first","affiliation":[{"name":"L\u2010NESS, Department of Physics Politecnico di Milano  Via Anzani 42 Como 22100 Italy"},{"name":"BioSense Institute University of Novi Sad  Dr Zorana \u0110in\u0111i\u0107a 1 Novi Sad 21000 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