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Electrospinning technology is attracting increasing interest for the fabrication of several polymeric and inorganic nanofibrous materials useful for a wide range of applications. Although the intensive research performed to understand the physics of the electrospinning process, control of polymeric jet path and of fibre deposition still remains a challenge. In this work, micropatterned electrospun materials with tunable porosity are fabricated by using novel collector devices made up of a steel sheet coated with a vitreous enamel layer. The novel approach permits to modulate electrical properties of the collector, acting on charge distribution and charge diffusion properties of the vitreous enamel coating, without introducing substantial modification of the electrospinning apparatus. The proposed solution allows the achievement of novel electrospun products for all those advanced applications requiring materials with suited fibre deposition such as, microelectronics, optical and photonic devices, as well as scaffolds for tissue engineering.