In this study, a multifunctional acoustic metastructure is proposed to achieve both effective low-frequency sound isolation and acoustic energy harvesting. A metallic substrate with proof mass is adopted to generate the local resonant phenomenon for the purpose of overcoming the drawbacks of the previous rubber film-based acoustic metastructure; the latter usually requires an elaborate tension process. Numerical simulations show that the proposed structure exhibits excellent noise isolation performance in the low-frequency band. Meanwhile, the incident sound energy can be converted into electrical energy with the help of an added piezoelectric patch. Numerical simulation results indicate that the harvested energy can reach the mW level. The parameters\textquotesingle influence on the metastructure\textquotesingle s vibro-acoustic and energy harvesting performance are discussed in detail. An optimized configuration is selected and used for experimental study. It is demonstrated that 0.21 mW electrical power at 155 Hz can be harvested by the proposed metastructure under 114 dB sound pressure excitation.