Surface-functionalized polymeric microspheres have wide applications in various areas. Herein, monodisperse poly(styrene–methyl methacrylate–acrylic acid) (PSMA) microspheres were prepared via emulsion polymerization. Polyaniline (PANI) was then coated on the PSMA surface via in situ polymerization, and a three-dimensional (3D) structured reticulate PANI/PSMA composite was, thus, obtained. The adsorption performance of the composite for organic dyes under different circumstances and the adsorption mechanism were studied. The obtained PANI/PSMA composite exhibited a high adsorption rate and adsorption capacity, as well as good adsorption selectivity toward methyl orange (MO). The adsorption process followed pseudo-second-order kinetics and the Langmuir isotherm. The maximum adsorption capacity for MO was 147.93 mg/g. After five cycles of adsorption–desorption, the removal rate remained higher than 90%, which indicated that the adsorbent has great recyclability. The adsorbent materials presented herein would be highly valuable for the removal of organic dyes from wastewater.