Aiming at the problem that most of the coal in the south six mining area of Xiqu Mine was destroyed by small kiln, and the water condition in the roadway of the old empty area was unclear, two geophysical prospecting methods, natural source audio magnetotelluric method and transient electromagnetic method, were used to detect the water-rich area in Goaf. The results of field Engineering application showed that these two geophysical prospecting methods confirm and supplement each other, accurately explored the distribution of water accumulation in goaf in this area, and the application effect was good, providing some experience and reference for the exploration of goaf in the rest of the group.