To overcome the problem caused by the lability of the Au-S bond, we demonstrate the first use of Mn-2(CO)(10) for visible-light-induced surface grafting polymerization on Au surfaces in this paper. The visible-light-induced surface grafting of poly(N-isopropylacrylamide) (PNIPAAm) has the features of a "controlled" polymerization, which is characterized by a linear relationship between the thickness of the grafting layer and the monomer concentration. Ellipsometry indicated the formation of PNIPAAm films of up to similar to 200 nm in thickness after only 10 min of polymerization at room temperature, demonstrating that this is a very fast process in comparison with traditional grafting polymerization techniques. Moreover, to demonstrate the potential applications of our approach, different substrates grafted by PNIPAAm and the covalent immobilization of a range of polymers on Au surfaces were also demonstrated. Considering the advantages of simplicity, efficiency, and mild reaction conditions as well as the ability of catecholic derivatives to bind to a large variety of substrates, this visible-light-induced grafting method is expected to be useful in designing functional interfaces.