Electrostatic Template-Assisted Deposition (ETAD) of microparticles is described as a new process to control the deposition of microparticles by electrospraying onto a substrate. It relies on the construction of an electrostatic template by electrospinning a thin layer of fibers onto a micropatterned collector. Because the fibers cannot release their charges when they are suspended over cavities of the micropatterned collector, an electrostatic template is formed with repulsive and attractive domains. This electrostatic template is then used to guide precisely the particle deposition during the electrospraying step. Microstructured bi-layer composites with a great variety of micropatterns can thus be elaborated with any kind of materials allowing the use of the ETAD process for a wide range of applications. As a proof of concept, the ETAD process was applied for the production of composite scaffolds with poly(ε-caprolactone) nanofibers covered by a micropatterned layer of hydroxyapatite. This scaffold was then embedded in a biochip containing 21 wells and used for MG-63 cell proliferation and mineralization studies, showing their possible application in the screening of the scaffold structure for tissue engineering.