A luminescent conjugated macrocycle polymer (CMP) with strong two‐photon fluorescence property, namely, P5‐TPE‐CMP, is constructed from ditriflate‐functionalized pillar5arene and a 1,1,2,2‐tetrakis(4‐ethynylphenyl)ethylene (TPE) linker through a Sonogashira–Hagihara cross‐coupling reaction. Significantly, in sharp contrast with the corresponding conjugated microporous polymer without synthetic macrocycles, P5‐TPE‐CMP shows an outstanding stability against photobleaching and exhibits highly selective cation sensing capability toward Fe3+ at different excitation wavelengths (both UV and red–near‐infrared regions). Meanwhile, its fluorescence could also be sufficiently quenched by 4‐amino azobenzene, a frequently used organic dye that is certified to be carcinogenic, as compared with a group of common organic compounds. This work paves a new way for enhancing the properties of porous organic polymers through the introduction of supramolecular macrocycles like macrocyclic arenes. Conjugated macrocycle polymers are first constructed from ditriflate‐functionalized pillararene and a 1,1,2,2‐tetrakis(4‐ethynylphenyl)ethylene linker through a Sonogashira–Hagihara cross‐coupling reaction. They show excellent two‐photon fluorescence (TPF) and serve as a highly efficient TPF sensor for metal ions and organic molecules.