Our study demonstrates a facile approach for the synthesis of metal NP-embedded freestanding polyelectrolyte complexes (PECs) without sacrificial templates, which can be used as nanoactuators, nanoshutters, and nanofilters. The metal NP-PECs were prepared by mixing metal precursor-preadsorbed cation and anion PEs, using a nonstoichiometric ratio, followed by a controlled heat treatment. The metal NP-PECs showed reversible structural changes such as shrinking or swelling when they were exposed to various pH conditions. During the changes, they were also able to reversibly control the interparticle distance of the metal NPs embedded in the PECs, which has allowed the easy tuning of their catalytic and optical properties. By the reversible control of structural changes, the PECs can also be used as nanoshutters to reversibly control the flow of nanomaterials in the channels or pores. Furthermore, metal NP-embedded PECs, Au/Ag-PECs, were demonstrated to be useful as nanofilters for removing or transforming unwanted materials.