A method of patterning using double exposure patterning in a liquid immersion lithographic process is provided. The patterning method comprises a step of forming a first pattern on a substrate using a first resist layer forming composition, a step of making the first pattern inactive, a step of forming a second pattern on a substrate on which a pattern has been formed using a second resist layer forming composition and exposing the second resist layer to radiation, and a step of developing the exposed resist layer to form a second pattern in the space area of the first pattern. The first resist layer forming composition contains a cross-linking agent which accelerates conversion of the first layer from positive-working to negative-working.