A series of Pt(II) N^N^C pincer complexes bearing isocyanide-styrene ligand in the fourth position was synthesized and their photophysics was studied in detail. In solution the complexes exhibit phosphorescence from 3MLCT excited state, whereas in solid state due to crystal packing effects all but one complexes display 3MMLCT emission accompanied by a considerable red shift of emission band, which may be ascribed to formation of binary aggregates with short Pt–Pt contacts. The styrene function of the isocyanide ligand allows complexes copolymerizing with polyvinylpyrrolidone via RAFT chemistry to give amphiphilic block copolymers with the hydrophobic block consisting of a few “back-to-back” copolymerized platinum complexes. In organic solvent, the copolymers exist as isolated molecular entities showing a limited intramolecular aggregation of the platinum chromophores analogous to their behavior in the solid state. On the contrary, in aqueous media hydrophobicity of the platinum containing blocks provokes formation of micellar type nanospecies, demonstrating intermolecular aggregation of the platinum chromophores with tighter contacts of the platinum centers and multiple character of the aggregates. This behavior results in much stronger red shift of emission into NIR area that makes the copolymers promising for application in biological experiments as NIR emitting probes.