An efficient method for preparing petroleum sulfonates is described in this article. Petroleum sulfonates were prepared from five different refinery cuts and characterized by infrarred and ultra-violet spectroscopy. Their hydrophilic-lipophilic relative afinity was assessed by performing phase behavior scans. The prepared surfactants were evaluated in formulations for Chemical Enhanced Oil Recovery (CEOR), showing that, under the evaluation conditions, the solubilization ratios increase with the structural similarity between the crude oil and the surfactant molecules. It was confirmed that, when used as secondary surfactants, the petroleum sulfonates here prepared allow to achieve relatively high solubilization parameters.