Polyethylene/polyethylene oxide (PE/PEO) blends with multiwall carbon nanotubes (MWNTs) were developed by melt mixing. The positive temperature co-efficient (PTC) and structural relaxations were systematically investigated by broadband dielectric spectroscopy. The localization of MWNTs in the blends was governed by flow characteristics. Negative temperature coefficient (NTC) effects were exhibited by neat blends while the blends with MWNTs exhibited both positive temperature co-efficient (PTC) and NTC effects. These findings were related to melting of crystallites and were also supported by differential scanning calorimeter (DSC). Due to differences in flow characteristics, process induced morphologies were observed in compression molded samples and were further supported by scanning electron and scanning acoustic microscopy (SAM) studies. Both surface and volume electrical conductivity on the samples also supported this fact. Interestingly, the segmental dynamics below and above the melting temperature of PE was significantly different in presence of MWNTs.