We have developed a high-sensitivity polypyrrole (PPy) film with a porous structure using a simple and easy method of doping thiol self-assembled monolayer (SAM)-Cu particles into a PPy film. The thiol-Cu-SAM particles were doped by the adsorption of thioxylenol or decanethiol into the porous PPy film surface, resulting in an improvement in sensitivity of the film to NH3. Owing to the addition of thiol-Cu-SAM particles formed using various 4-tert-butylcalix-6-arene thiol derivatives, the sensitivity correspondingly decreased. In particular, for the case of poly(propylene oxide)-calix-6-arenethiol, a marked decrease in sensitivity was observed. Using this composite nanomaterial, we found that the detection limit for NH3 increased to concentration levels of several ppm. We present a novel preparation method for these sensor films aimed at controlling their porosity and sensitivity.