We employed in-situ spectroscopic ellipsometry(SE) and imaging ellipsometry(IE) to study the interaction of water and photoresist(PR) in 193 immersion lithography. Real time measurement of SE showed thickness increase when PR was immerged in water indicating swelling effect. From the temporal evolution we could observe its reaction-limited behavior. Meanwhile, IE could identify the modification of PR surface by contact of water even for a short period of a second.