This work assesses the use of immobilized humic acid (ImHA) onto aminopropyl silica (APS) as a sorbent for the removal and preconcentration of trace amounts of cobalt ions by on-line solid phase extraction (SPE) technique in the column system prepared in our laboratory. Different parameters, such as the effect of the pH, concentration, and flow rate, were studied and throughput was observed by a UV detector. All SPE steps were monitored by breakthrough curves used to visualize distribution of cobalt concentration between mobile and solid phase. The solutions collected from stripping steps were analyzed in atomic absorption spectrometer (AAS) and the amount of sorbed ions was calculated. Sorption characteristics were evaluated by using common adsorption isotherms and Scatchard plot analysis. From the obtained results, it was seen that sorption mechanism of cobalt ions were fitted to Langmuir model on a large scale and thought to be localized. Mean free energy (E∈=∈40.82 kJ mol -1) calculated from D-R isotherm showed that chemical interactions are more effective than physical interactions. This investigation reveals a new, simple, environmentally friendly, and cost-effective method for removal and preconcentration of cobalt ions from aqueous solutions by a new aminopropyl silica-immobilized humic acid material. © 2012 Springer Science+Business Media B.V.