A facile method for rapid fabrication of micrometre-thick films with hierarchical micro- and nanostructures was developed by layer-by-layer (LbL) deposition of hydrogen-bonded complexes of poly(vinylpyrrolidione) (PVPON) and poly(acrylic acid) (PAA) (denoted PVPON&PAA) with poly(methacrylic acid) (PMAA). FT-IR spectroscopy confirmed that hydrogen-bonding interactions between the PVPON of PVPON&PAA complexes and PMAA was the driving force for the successful construction of the LbL assembled PVPON&PAA/PMAA films. A non-drying film preparative process was critically important to realize the rapid fabrication of PVPON&PAA/PMAA films with hierarchical micro- and nanostructures because the structure of the adsorbed spherical PVPON&PAA complexes can be well preserved during film fabrication which led to an exponential growth of the PVPON&PAA/PMAA films. After chemical vapor deposition of a layer of fluoroalkylsilane on top of the as-prepared PVPON&PAA/PMAA films with hierarchical micro- and nanostructures, superhydrophobic coatings were conveniently fabricated. The use of polymeric complexes as building blocks for LbL film fabrication not only provides a facile method for the rapid fabrication of micrometre-thick films, but also enables the convenient tailoring of film structures because of the structural diversity of polymeric complexes in solution.