This report deals with space charge behavior in PE (polyethylene) under dc fields. Direct observation of time-dependent space charge profiles in 3-mm thick XLPE (crosslinked low-density polyethylene) cable insulation under dc electric fields was performed using the pulsed electroacoustic method. Stable hetero charges were formed when the field was as low as 0.2 MV/cm, and intermittent generation of packet shaped space charges and their propagation through the insulation were observed when the field was as high as 0.7 MV/cm. These phenomena were reproduced in sheet specimens of XLPE and LDPE (low-density polyethylene). It was found that hetero charges resulted from heat treatment of the XLPE specimen containing antioxidant and acetophenone, which is one of the crosslinking by-products, suggesting dissociation of the antioxidant through solvation at high temperature by acetophenone. The packet charges were easily detected when acetophenone was diffused into the LDPE specimen. However, uniformity of acetophenone distribution prevented the packet charge generation. It is suggested on the basis of several experimental results that local ionization of impurities in the insulation through solvation by acetophenone takes place assisted by high field and leads to the packet charge generation. A numerical simulation was carried out based on the above model.