Polypyrrole (PPy) and its derivatives containing different aromatic segments were synthesized by the interfacial polymerization reaction using ammonium per sulfate as oxidant, and were characterized by using Fourier transform infrared, Ultraviolet/visible absorption, and Raman spectroscopic techniques. The third-order nonlinear optical properties of all samples were measured by using nanosecond Z-scan measurements at 532 nm. At the identical mass concentration of 0.15 mg•mL −1 , all PPy derivatives exhibited an obvious reverse saturable absorption performance, while the saturable absorption response was observed for PPy. In addition, significant differences in their nonlinear optical performances were observed, highlighting the influence on optical nonlinearity of the aromatic segments of conjugated polymers.