In this paper, for the first time, a TiO2 submicron-diameter wire suspension-based smart window device is demonstrated in which combined planar and finger electrodes are utilised to reversibly change the orientation of the nanowires. Electrospun TiO2 anatase submicron-diameter wire suspensions in a viscous polydimethylsiloxane (PDMS) matrix were prepared directly from electrospun submicron-diameter fibre mats by using high-shear mixing, achieving the complete break-up of all electrospun mats and suspending TiO2 submicron-diameter wires uniformly in the PDMS matrix. Suspension was used as an active layer in an electro-optical device where a reversible change in light scattering is achieved by preparing a device consisting of an active layer and combined planar and finger electrode system. Using the constructed device, it was possible to change the alignment or spatial distribution of TiO2 submicron-diameter wires by applying a DC electric field across the planar or finger, electrodes thus changing the transmittance (DT = 25%) of the suspension and demonstrating the potential to use combined planar and finger electrode devices in smart window applications.