In the current study, we propose an efficient thermodynamic method to precisely control multi-walled carbon nanotubes (MWCNTs) at the interface of a co-continuous PS/PMMA blend to design conductive polymer composites with ultralow percolation threshold. The achievement of the interfacial distribution of MWCNTs is attributed to the balance of p-p interactions between PS and MWCNT surfaces and dipoledipole interactions between PMMA and carboxyl groups on MWCNT surfaces. It is found that MWCNTs can be well controlled at PS/PMMA interface when carboxyl content on MWCNT surfaces is ca. 0.73 wt%, which can exactly make a balance between p-p interactions and dipole-dipole interactions. Because all

the MWCNTs are precisely controlled at the continuous interface to build a percolated conductive pathway, the percolation threshold of this type of conductive polymer composite is lowered from 1.81 wt  (MWCNTs/PS) or 1.46 wt% (MWCNTs/PMMA) to 0.017 wt%, which is an ultralow percolation threshold so far. More importantly, this method can be easily extended to other systems involved with p-p interactions and dipole-dipole interactions.