We present the discovery of a novel and intriguing global geometric structure of the (interior) transmission eigenfunctions associated with the Helmholtz system. It is shown in generic scenarios that there always exists a sequence of transmission eigenfunctions with the corresponding eigenvalues going to infinity such that those eigenfunctions are localized around the boundary of the domain. We provide a comprehensive and rigorous justification in the case within the radial geometry, whereas for the non-radial case, we conduct extensive numerical experiments to quantitatively verify the localizing behaviours. The discovery provides a new perspective on wave localization. As significant applications, we develop a novel inverse scattering scheme that can produce super-resolution imaging effects and propose a method of generating the so-called pseudo surface plasmon resonant (PSPR) modes with a potential sensing application.