Abstract: Three meso-tetrakis(4-n-acyloxylphenyl) porphyrins and their platinum(Ⅱ) complexes were synthesized.The structures of the compounds and photophysical properties were characterized by ¹H NMR,MS,UV-Vis and photoluminescence(PL) spectroscopies.Differential scanning calorimetry(DSC) and polarizing microscope were used to probe liquid properties of the complexes.Strong triplet emission peaks at around 660 nm were observed with phosphorescence quantum efficiencies(0.183~0.211) in THF solution and triplet lifetime(8.86~13.52 μs) in degassed CH₂Cl₂ solution.The results show that the attached acyloxy of the long carbon chains at the meso-positions of tetrakis(4-hydroxylphenyl) porphyrin can reduce phosphorescent lifetime and aggregation between molecules.Further,these complexes reveal characteristic of liquid crystal for long carbon chain acyloxy at the meso-positions of porphyrin complexes.It is possible that these new complexes can be used as applicable phosphorescent emitters in organic light emitter devices(OLEDs) and polarized luminescent devices.