Electrochemical sensors are attracting great interest for their different applications. To improve their performances, basic research focuses on two main issues: improve their metrological characteristics (e.g., repeatability, reusability and sensitivity) and investigate innovative fabrication processes. In this work, we demonstrate an innovative microstructuration technique aimed at increasing electrochemical sensor sensitivity to improve electrode active area by an innovative fabrication technique. The process is empowered by aerosol jet printing (AJP), an additive-manufacturing and non-contact printing technique that allows depositing functional inks in precise patterns such as parallel lines and grids. The 3D printed microstructures increased the active surface area by up to 130% without changing the substrate occupancy. Further, electrochemical detection of ferro/ferri-cyanide was used to evaluate the sensitivity of the electrodes. This evaluation points out a sensitivity increase of 2.3-fold on average between bare and fully microstructured devices. The increase of surface area and sensitivity are well linearly correlated as expected, verifying the fitness of our production process. The proposed microstructuration is a viable solution for many applications that requires high sensitivity, and the proposed technique, since it does not require masks or complex procedures, turns out to be flexible and applicable to infinite construction geometries.