In this paper, we report on the fabrication of 2D silver nanodendrites on silicon chips by electrochemical deposition at platinum microelectrodes. The dendritic structuring can be explained by the interplay of electromigration and diffusion of silver ions. Characterisation of the modified electrode by cyclic voltammetry revealed the deposited silver nanostructures were not electrically connected to the original microelectrode. High resolution imaging revealed the sample had a high density of nanostructures and nanogaps, necessary for SERS effect to occur. Raman reporter 4-ABT was used to calculate an enhancement factor of c.a. 10 6 . Density functional theory (DFT) simulations were revealed the interaction between herbicide MCPA and silver surface was weak. To increase this interaction, the silver nanodendrites were functionalised with thiolated cyclodextrin, and SERS based detection of the pesticide reported. This concept can be extended to other contaminants with low affinity to silver.