Polyelectrolyte multilayer films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) and PAH/ poly(sodium 4-styrenesulfonate) (PSS) based on electrostatic interactions as a driving force are patterned by room-temperature nanoimprint lithography (RT-NIL). Under an imprinting pressure of 40 bar for 8 min, well-defined pattern structures with a line width of approximate to 330 nm and a separation of approximate to 413 nm are achieved. Meanwhile, hydrogen-bonding-directed multilayer films of poly(vinyl pyrrolidone) (PVPON)/ poly(methyl acrylic acid) (PMAA) and poly(4-vinylpyridine)/ PAA can also be patterned in a similar way by RT-NIL. The successful imprinting of these films originates from the high compressibility and fluidity of the layered polymeric films under high pressure.