The spreading characteristics of volatile liquid film on the liquid-solid substrate have been experimentally investigated. Unlike the liquid film spreading on the liquid substrate, there exists a dip at the top of the solid substrate, as a result, the spreading behaviors are inhibited. It is found that dip characteristics of R’/ R slightly decrease at the beginning then it keeps constant R’/ R=0.83 until the end. Moreover, the comparison of spreading behaviors on two different substrates is investigated. When the volatile film spreads on the liquid-solid substrate, the maximum radii of the outer and inner rings are smaller, but the process lasts longer. Although the evolutions of radii are different, the variation trend of nondimensional ring width is consistent. We further study the spreading rate; results show there exist three stages due to the relative importance of different forces. Our results provide important missing pieces to the rich mechanisms of the multiple-phase flow driven by the Marangoni effect.