A method is provided which is capable of efficiently taking most of a precious sample into an extraction vessel without wasting when the sample is extracted from a collection section of a sampling rod. The method includes the steps of collecting a sample using a sampling rod formed of a rod body and a collection section attached to the rod body, inserting the sampling rod into the extraction vessel, placing the rod body in a gap formed in a grappling hook section which is disposed in an insertion path of the sampling rod, the gap having a width smaller than a diameter of the collection section and being capable of receiving the rod body, withdrawing the rod body with the rod body being placed in the gap and detaching the collection section from the rod body by hooking the collection section to the grappling hook section.