A new sulfation technique was developed using DMF-katastaltic chlorosulfonic acid as sulfation/sulfonation agent which showed higher selectivity of sulfation against sulfonation for the feedstocks containing both aromatic ring and hydroxyl intramolecularly. Nonylphenol polyproxylene ether sulfate (NPPS), one of the extended surfactant was highly selectively synthesized from nonylphenol polyproxylene ether (NPP) by using the aforementioned technique. The influential factors such as dosages of sulfation agent, ageing temperatures and ageing times were systematically investigated. The selectivity of sulfation could reach to 100 % and the maximum yield was as high as 98.4 % under the optimal conditions of 1.3:1 molar ration of HSO3Cl to NPP at 35 oC reacting 15 min. And fortunately DMF could be simply recovered and reused. The experimental results showed that it was difficult to obtain high sulfation selectivity by only using chlorosulfonic acid as sulfation agent. And it is also showed that compared with sulfamic acid as sulfation agent, this technique was much simple, more efficient and more inexpensive. It is expected that the novel technique is a hopeful sulfation method with high sulfation selectivity for the other feedstocks containing both aromatic ring and hydroxyl intramolecularly.