Over the past decade, on-surface fabrication of organic nanostructures has been widely investigated for the development of molecular electronic components, catalysts, and new materials. Here, we introduce a new strategy to obtain alkyl oligomers in a controlled manner using on-surface radical oligomerisations that are triggered by electrons between the tip of a scanning tunnelling microscope and the Si(111)√3 ×√3 R30°-B surface. This electron transfer event only occurs when the bias voltage is below −4.5 V and allows access to reactive radical species under exceptionally mild conditions. This transfer can effectively ‘switch on’ a sequence leading to the formation of oligomers of defined size distribution thanks to the on-surface confinement of the reactive species. Our approach enables new ways to initiate and control radical oligomerisations with tunnelling electrons, leading to molecularly precise nanofabrication.