A resonance light-scattering method (RLS) for the determination of Rh(III) was initially developed, based on the reaction among Rh(III), WO42− and ethylrhodamine B. The method possesses high sensitivity, but lacks selectivity. Therefore, a Rh(III) ion-imprinted polymer (IIP), prepared by precipitation polymerization using 2-(allylthio)nicotinic acid (ANA) as functional monomer, was used as sorbent to construct a ion-imprint based solid-phase extraction (IIP-SPE) method for separation of rhodium from complicated matrices prior to its determination by RLS. The experimental parameters affecting the extraction efficiency and selectivity of IIP-SPE were studied carefully. Under the optimal conditions, the IIP-SPE column with the enrichment factor (EF) of 10 could be used at least 20 times without decreasing its extraction recovery (above 90%) significantly. The calibration graph for the determination of rhodium by RLS coupled with IIP-SPE procedure was linear in the range of 0.06–1.5ngmL−1 with the detection limit of 0.024ngmL−1. There is no metal ions tested at the concentration below 10ngmL−1 interfered in the determination of 0.8ngmL−1 Rh(III). The proposed IIP-SPE–RLS method was successfully applied to the extraction and measurement of trace rhodium in catalyst, water and geochemical samples with the relative standard deviation (RSD) of less than 4.0% (n=4).