Due to their exceptional orientation of 2D nanofillers, layer-by-layer (LbL) assembled polymer/graphene oxide thin films exhibit unmatched mechanical performance relative to any conventionally produced counterparts with similar composition. Unprecedented mechanical property improvement, by replacing graphene oxide with pristine graphene, is demonstrated in this work. Polyvinylpyrrolidone-stabilized graphene platelets are alternately deposited with poly(acrylic acid) using hydrogen bonding assisted LbL assembly. Transmission electron microscopy imaging and the Halpin-Tsai model are used to demonstrate, for the first time, that intact graphene can be processed from water to generate polymer nanocomposite thin films with simultaneous parallel-alignment, high packing density, and exfoliation. A multilayer thin film with only 3.9 vol% of highly exfoliated, and structurally intact graphene, increases the elastic modulus (E) of a polymer multilayer thin film by 322% (from 1.41 to 4.81 GPa), while maintaining visible light transmittance of approximate to 90%. This is one of the greatest improvements in elastic modulus ever reported for a graphene-filled polymer nanocomposite with a glassy (E > 1 GPa) matrix. The technique described here provides a powerful new tool to improve nanocomposite properties (mechanical, gas transport, etc.) that can be universally applied to a variety of polymer matrices and 2D nanoplatelets.