Fluorescence imaging can be employed in fields of medical treatment, astronomical exploration, and national defense security. Traditional fluorescence imaging often takes the single-photon techniques, which is vulnerable to background interference and photobleaching. Remedially, two-photon fluorescence imaging can achieve much higher-resolution fluorescence imaging for reducing scattering and deeper depth. Hence, by assembling the tetraphenylethylene backbones with nontoxic and non-noble K⁺ ions, compound 1 ([(Hdma)K(H₂ettc)]_n, H₄ettc = 4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-4-carboxylic acid))) with the crystallization-induced emissions exhibited charming fluorescence imaging under two-photon excitation microscopy (TPEM). Besides, luminescent powders based on compound 1 can achieve high-resolution fingerprint recognition, providing secure access control and identification for a novel authentication method. Compared with the commercial fluorescent dyes coumarin-6, the as-synthesized compound 1 showed great solvent stability, indicating its durability against harsh environment. Moreover, compound 1 shows mechanoluminescent properties for the perturbation of weak supramolecular interactions within ordered arrangements of the H₂ettc²⁻ ligands. This novel compound has provided an important insight to the development of two-photon fluorescence imaging and advanced external-stimuli responsive materials.