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Anharmonic lattice vibration in metallic and semiconducting Sb2Te3 is investigated using temperature dependent Raman spectroscopic studies, synchrotron powder diffraction, and heat-capacity measurements. Thermal variation of structural parameters divulges temperature dependence of structural anisotropy in both the samples. It is revealed that semiconducting Sb2Te3, having higher defect density and larger phonon anharmonicity, possesses lower thermal conductivity. As compared to its metallic counterpart, significant increase in thermoelectric figure of merit, ZT is reported for the semiconducting Sb2Te3. Correlation among structural anisotropy, phonon anharmonicity and ZT is established.