Polypyrrole (PPy) nanowire networks have been synthesized in high yield (higher than 90%) by chemical oxidative polymerization of pyrrole in the presence of hexadecyltrimethylammonium bromide (HTAB) and organic diacids (oxalic acid, tartaric acid, or glutaric acid) and triacid (citric acid). The diameter of nanowire is 60-90 nm. The influence of reaction conditions, such as polymerization temperature, polymerization time, and the molar ratios of HTAB to organic acids and pyrrole, on the morphologies of the PPy nanowire networks has been systematically investigated. In addition, the interconnected PPy nanoparticles are prepared without using HTAB. The film of PPy nanowire networks and nanoparticles is superhydrophilic. A plausible formation mechanism of PPy nanowire networks is discussed.