Polyester/polylactone polyols with of without benzoic acid unit were synthesized by polycondensation of polycaprolactone 0201, trimethylolpropane, adipic acid, and benzoic acid. Then, two-packaged polyurethane coatings with three dimensional network structure were prepared by curing the produced polyols with TDI-isocyanurate at ambient temperature. Various tests on the coating properties of the prepared coatings showed a remarkable improvement in the physical properties. The introduction of polycaprolactone 0201 as diol in the polyurethane coatings improved the cross hatch adhesion, flexibility, impact resistance, and hydrocarbon resistance of coatings. Changes in the drying and curing behavior with the contents of benzoic acid suggest that they have reasonable coating properties, such as drying time of 2 to 4 hours and pot-life time of 18 to 39 hours.