In this work, highly conductive Al-doped ZnO (AZO) films are deposited on transparent and flexible muscovite mica substrates by using the atomic layer deposition (ALD) technique. AZO-mica structures possess high optical transmittance at visible and near-infrared spectral range and retain low electric resistivity, even after continuous bending of up to 800 cycles. Structure performances after bending tests have been supported by atomic force microscopy (AFM) analysis. Based on performed optical and electrical characterizations AZO films on mica are implemented as transparent conductive electrodes in flexible polymer dispersed liquid crystal (PDLC) devices. The measured electro-optical characteristics and response time of the proposed devices reveal the higher potential of AZO-mica for future ITO-free flexible optoelectronic applications.