Mueller matrix ellipsometry has been used to determine the effective optical constants of island-like Ag films deposited by thermal evaporation. These films depart substantially from bulk silver with a prominent localized surface plasmon resonance. Moreover, despite the isotropic appearance, they exhibit uniaxial optical properties with the optical axis inclined by 83.4° from the substrate normal toward the direction of the incoming vapor flux. The uniaxial model supports the plasmon resonance peaks revealed by in-plane absorbance measurements of the films. The uniaxial behavior suggests that the resonances along the ordinary axes are weakly coupled between neighboring particles, whereas the extraordinary resonance is relatively strongly coupled. Therefore, the anisotropy should be considered in the practical applications of these plasmonic films.