The optimization of biosensing efficiency on a diamond platform depends on the successful coupling of biomolecules on the surface, and also on effective signal transduction in the biorecognition events. In terms of biofunctionalization of diamond surfaces, surface electrochemical studies of diamond modified with undecylenic acid (UA), with and without headgroup protection, were performed. The direct photochemical coupling method employing UA was found to impart a higher density of carboxylic acid groups on the diamond surface compared to that using trifluoroethyl undecenoate (TFEU) as the protecting group during the coupling process. Non-faradic impedimetric DNA sensing revealed that lightly doped diamond gives better signal transduction sensitivity compared to highly doped diamond.