Two novel porphyrinic compounds, {Zn[TCPP(CH2CH3)2(CH3)2]}n (1) and TCPP(CH3)4 (2) (TCPP = meso-tetra(4-carboxyphenyl)porphyrin), with the TCPP(CH2CH3)2(CH3)2 and TCPP(CH3)4 generated in situ, have been synthesized via a solvothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 is characteristic of a two-dimensional (2-D) coordination polymer, based on the zinc ion coordinating to four nitrogen atoms and two oxygen atoms. Compound 1 possesses a large void space (220 Å3) corresponding to 4.6% of the unit-cell volume. Compound 2 is characterized by an isolated structure. The reaction mechanism of preparing both compounds was explored. The photoluminescence properties, FT-IR, UV-vis absorption spectra, fluorescence lifetime and fluorescence quantum yield of TCPP were also reported.