We found that liquid droplets encapsulated by Parylene deposited directly on a liquid surface deformed toward spherical shapes during Parylene deposition. This deformation suggested that the film stress was tensile. We calculated the film stress of such Parylene films by studying the surface mean curvature of the droplet shape and found the film stress measured about 0.7-0.9 MPa tensile. This film stress is of opposite type to that of as-deposited Parylene films deposited on solid substrates, which was compressive. This difference might indicate a profound change of the Parylene polymer due to the use of liquid surface as deposition substrate. The tensile film stress and its effect on the droplet shape also have implications in the fabrication and operation of Parylene microdevices that have encapsulated liquid structures such as microlens or micropumps.