A new approach for polytriarylamine (PTAA)-assisted selective dispersion for single-walled carbon nanotubes (SWNTs) in a toluene solution has been developed. The triarylamine-based conjugated polymers are able to selectively wrap the SWNTs with specific chiral indices depending on their backbone structures (e.g., PTAA(12), PTAA(12)-P, and PTAA(12)-BP) and side-chain functionality (e.g., PTAA(6), PTAA(6)-alt-PTAA, and PTAA(12)-alt-PTAA). PTAA exhibits highly selective wrapping for the (6,5) chirality from CoMoCAT (catalytic processes) SWNTs but low selectivity in a dispersion of HiPCO (high-pressure carbon monoxide) SWNTs. Therefore, the selection for HiPCO SWNTs has been further improved via PTAA(12)-alt-PTAA wrapping with alternating side chains and mainly exhibits a high affinity to (6,5) SWNTs with high chiral angles (>= 24.5 degrees). The wrapping conformation and binding energy of the polymer/(6,5) SWNTs were studied via molecular modeling, and the simulated results are in good agreement with the experimental data for the selective dispersion of (6,5) SWNTs.