In this study, the construction of macroscopic segregated CNTs network is achieved by a simple melt coating method. In the process, poly(l‐lactic acid) (PLA) is chosen as the polymer matrix and poly(propylene carbonate) (PPC) is chosen as a carrier polymer for CNTs and an interfacial compatilizer for segregated PLA domains. Thanks to the random distribution of CNTs in coating layer and the formation of macroscopic segregated CNTs network, the percolation threshold is reduced to be as low as 0.026 vol%. So far as we know, this is the lowest percolation threshold that can be obtained in segregated conductive polymer composites (CPCs) with pristine CNTs as conductive fillers. Moreover, thanks to the adhesive effect of PPC located between the boundaries of PLA domains, the as‐prepared CPCs show an excellent balance between conductivity and mechanical properties. This simple method is low‐cost and time efficient, which is especially suitable for industrial applications. POLYM. COMPOS., 39:841–847, 2018. © 2016 Society of Plastics Engineers