Such coupling can induce significant red-shifts in LSPR spectra and create greatly enhanced electromagnetic fields, both of which endow plasmonic assemblies with dramatically different optical properties compared to single PNC counterparts. [43,[48][49][50] Small molecular surfactants (i.e., hexadecyltrimethylammonium bromide-CTAB), [51] silica, [52][53][54] biomacromolecules (e.g., DNA), [55][56][57][58][59] and synthetic polymers are the most commonly used surface coatings for PNCs, [60,61] imparting surface functionalities to direct their selfassembly. Small molecular surfactants are able to provide decent stability in dielectric environments (e.g., aqueous solution), although their relatively small sizes makes it difficult to control interparticle spacing or intraparticle gap sizes. Both silica and DNA have been used as "spacers" for the SERS and fluorescence signal enhancement, but inherent size limits hold back their further extended uses. For example, the silica coating is difficult for building a gap of smaller than 10 nm, [52,62] while DNA has not demonstrated its utility in realizing a relatively large nanogap (i.e., >2 nm). [57,59] Consequently, such size-tuning limitation makes them challenging to offer sufficient structural flexibility to tailor the LSPR, which is crucial for obtaining an optimal enhancement effect (e.g., fluorescence enhancement). [52,63,64] Moreover, the coassembly of DNA and PNC is primarily based on the base-pairing recognition, [58,65,66] which is too specific for the extensive uses.In contrast, there are a number of benefits in conjugating polymers with PNCs to direct their self-assembly: i) The conformation transformation of polymer chains provides the driving force for self-assembly. [43,45,48,[67][68][69] For example, the amphiphilic single-component or mixed polymer brushes anchored onto the PNCs can afford amphiphilicity-driven self-assembly to produce a library of assemblies including core-shell structure, Janus nanoparticles (JNPs), nanocluster, nanochain, lamellae, and vesicle. ii) The polymeric corona protects the PNC core and stabilizes the assemblies in dispersion media. [68,70,71] iii) By using stimuli-responsive polymer coatings, the formed assemblies can readily undergo structural changes in response to the external triggers. [15,[72][73][74][75][76] Moreover, the strength of interactions between polymer/PNC hybrid materials and external stimuli can be adjusted by varying the structures of the polymer coating, such as molecular weight (M w ) of the polymer. The large-sized polymer coating leads to more significant multivalent effects compared to small molecular ligands. iv) Also important is Plasmonic Nanocrystals Self-assembly of plasmonic nanocrystals (PNCs) and polymers provides access to a variety of functionalized metallic-polymer building blocks and higher-order hybrid plasmonic assemblies, and thus is of considerable fundamental and practical interest. The hybrid assemblies often not only inherit individual characteristics of polymers and PNCs but also exhi...