Synthesis of a new porous cobalt based metal-organic framework, [Co6(oba)6(CH3O)4(O)2]n·3DMF (TMU-11) has been carried out to introduce a new and highly efficient adsorbent of dibenzothiophene (DBT). This compound has been synthesized by solvothermal method using a nonlinear dicarboxylate ligand and characterized by single-crystal X-ray crystallography. To study the adsorption properties of the synthesized compound, TMU-11, for DBT removal, various factors, such as amount of adsorbent, contact time and temperature were examined. On the basis of the results, maximum efficiency and reusability in DBT removal occur under the mild reaction conditions. Furthermore, the DBT removal follows the pseudo-second order reaction kinetic. The maximum adsorption value is 825 mg/g. The selectivity test of DBT over naphthalene (NA) clearly shows that π−π interactions between organic linkers of TMU-11 and the aromatic ring of DBT are not responsible for the adsorption desulfurization (ADS) process and the main part of adsorption takes place on unsaturated site around Co centres. Our findings may provide some insight into the preparation of the adsorbent with superior performance in practical applications.