We have previously demonstrated that heme, iron(III)-protoporphyrin IX complex, and a parallel-quadruplex DNA assembled from d(TTAGGG) form a stable coordination complex called "heme-DNA complex". The heme-DNA complex exhibits a variety of spectroscopic characteristics remarkably similar to those of met-form of myoglobin, oxygen-binding hemoprotein, reflecting that the heme environments in the two systems are highly alike to each other. In a course of our effort toward exploring functional properties of the heme-DNA complex, we have investigated binding of gaseous molecules such as CO and O(2) to the heme-DNA complex. The present study revealed that the heme-DNA complex exhibits ability to accommodate these molecules as exogenous ligands.