Two-photon excitedf luorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connectingo ne, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl p-bridges, conjugated multipolar molecules TAT-(ZnP) n (n = 1-3) were developed as TPEF materialsf or cell imaging. The three new dyes presenth igh fluorescence quantum yields (0.40-0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPAc ross sectiono fTAT-ZnP (436 GM) is significantly largert han that of the ZnP reference (59 GM). The d TPA values of TAT-(ZnP) 2 and TAT-(ZnP) 3 further increase to 1031 and up to 1496 GM, respectively,i ndicatingt he effect of incorporated ZnP units on the TPA properties. The substantial improvemento ft he TPEF properties is attributed to the formation of p-conjugated quadrapole/octupole molecules and the extensiono fD-p-AD systems,w hich has been rationalized by density function theory(DFT) calculations. Moreover, all of the three new dyes displayg ood biocompatibility and preferential targeting ability towardc ytomembrane, thusc an be superior candidates for TPEF imaging of living cells. Overall, this work demonstratedapromisings trategy for the development of porphyrin-based TPEF materials by the construction and extensiono fD-p-AD multipolar array.