Dielectric material is an important material for film capacitors. However, the progress of this material is either impeded by its low dielectric constant, high loss tangent, or insufficient flexibility. In this work, PVA/GO film with alternating layer structure was fabricated by Spin-Coating-Assembly (SCA) method. This alternating layer structure not only benefits forming numerous microscale capacitors which improve ε value a lot, but also helps eliminate perpendicular contact of GO and prevents the formation of conductive pathways. Thus, compared with pure PVA, significantly increased dielectric permittivity and a low loss tangent were simultaneously observed for the PVA/GO film. The ratio of dielectric permittivity to loss tangent increased from 68 to 165. These films might be potential flexible dielectric materials for advanced electrical devices such as embedded capacitors.