We investigated experimentally the morphological evolution of thin polydimethylsiloxane films sandwiched between a silicon wafer and different bounding liquids with interfacial tensions varying by 2 orders of magnitude. It is shown that increasing the compatibility between film and bounding liquid by adding a few surfactant molecules results in a faster instability of shorter characteristic wavelength. Inversely, based on the characteristic parameters describing the instability we determined extremely small interfacial tensions with a remarkable accuracy.