Metal-free catalysts are preferred during these days in organic synthesis or in polymeriza- tions. Sulfonic acid is reported to be efficient in catalyzing reactions between isocyanates and alcohols. In this work, synthesis of sulfonic acid immobilized organic nanoparticles (nanoacid) and its application in catalyzing urethane formation, are elaborated. The nanoacid can be simply prepared by miniemulsion polymerization with a reactive surfacrant, namely sodium 4-((perfluoronon-8-en-l-yl)oxy)benzenesulfonate, followed by an acidification. From the images of scanning electron microscope, the nanoacid obtained is found to be narrowly dispersed and the average diameter is around 90 nm. The measured sulfur content is 0.5%, from which the content of sulfonic acid in the nanoparticles is calculated to be 0.16 mmol/g. When catalyzing urethane formation based on hexamethylene diisocyanate and n-butanol, the nanoacid catalyst exhibits considerable efficiency.