Polyurethane (PU)-based composite films containing highly aligned graphene sheets are produced through an environmentally benign process. An aqueous liquid crystalline dispersion of graphene oxide (GO) is in situ reduced in PU, resulting in a fine dispersion and a high degree of orientation of graphene sheets. The PU particles are adsorbed onto the surface of the reduced graphene oxide (rGO), and the rGO sheets with a large aspect ratio of over 10 000 tend to self-align during the film formation when the graphene content is high enough, say more than 2 wt%. The resulting composites show excellent electrical conductivity with an extremely low percolation threshold of 0.078 vol%, which is considered one of the lowest values ever reported for polymer composites containing graphene. The electrical conductivity of the composites with high graphene contents presents significant anisotropy due to the preferential formation of conductive networks along the in-plane direction, another proof of the existence of the self-aligned, layered structure.