The invention discloses a sample structure and a method for measuring ionization and charge transfer parameters of an insulating material. The sample structure is composed of a first barrier material,a measured material and a second barrier material, uses the barrier materials having the conductivity much lower than the measured material and having a high implantation threshold, and enables the charge injection of the barrier electrode to the sample and the outward migration of the charge in the measured material. The measuring method adopts an improved pulsed electro-acoustic (PEA) space charge measuring device, puts the measured sample structure into the measuring device, heats the sample structure to a specified temperature through a constant temperature circulating oil bath, and measures space charge characteristics generated by ionizing the material in the sample of the measured material under the conditions of the temperature and electric field by the PEA method. The sample structure and method provided by the invention primarily measure the space charge characteristics produced by ionization in an insulating material.