This paper presented the measurement results of space charge distribution and high field conduction in cross-linked polyethylene (XLPE) plate sample at various electric fields for a broad temperature range from 30 to 90 °C. The temperature effect on charge trapping and transport mechanism is discussed based on estimation of threshold characteristic and apparent mobility. It is shown that the threshold field for space charge accumulation apparently decreased with the temperature, probably associated with acceleration of charge injection and ionic dissociation. The apparent mobility of charges showed an exponential dependence on temperature, which indicates enhancement of charge detrapping and transfer rate at higher temperature. The field dependence of the space charge decreases with the temperature, results in more space charge accumulate at room temperature than at high temperature at certain high field. This behavior indicates that the space charge formation rate increases slower than the charge detrapping rate as the temperature increases. Besides, negative charge is always dominant in the sample at the measuring field and temperature range. This is probably due to stronger electron injection at XLPE-aluminum interface or more negative ion formed by dissociation of chemical species.