With the absence of on-situ temperature monitoring of optical fiber composite overhead ground wire (OPGW) for the process of sleet-thawing, early temperature warning and safety control of direct current (DC) in sleet-thawing process is difficult. Here we propose a Brillouin optical time-domain reflectometry (BOTDR) with broadband receiving for fast measurement and with distributed Raman amplification for long distance measurement of about 100 km. A field experiment for on-situ temperature monitoring of sleet-thawing of OPGW is also reported, which shows uneven change of temperature along the OPGW. The difference between the maximum and the minimum temperature change can be greater than 40 °C.