Poly(4-diphenylaminostyrene) (PDAS)-poly(1-vinylpyrene) (PVPY) binary block copolymers were synthesized by well-controlled anionic polymerization of 1-vinylpyrene for the first time. The nucleophilicity and solubility of the initiator system and poly(1-vinylpyrenyl) lithium were very important factors in the polymerization reaction. An initiator system of the poly(4-diphenylaminostyryl)lithium/ N,N,N',N'-tetramethylethylenediamine system in toluene was found to be very effective. The PDAS-PVPY binary block copolymer having a high molecular weight PVPY block acted as a non-covalent cross-linker for single-walled carbon nanotubes (SWNTs) gel due to the aggregation of the polymer chain in addition to the strong p-p interactions between pyrenyl groups and SWNTs, forming a self-assembled polymer/SWNTs nanocomposite. (C) 2016 Elsevier Ltd. All rights reserved.