The present invention provides an apparatus for highly accurate and real-time photoelectric glass substrate identification. The apparatus includes: a laser device for emitting a laser beam; a glass substrate that has a first surface and a second surface and is configured to receive the laser beam to generate a first laser beam point and a second laser beam point; and, a charged coupled device (CCD) camera inspecting equipment. The first laser beam point has a first point area, and the second laser beam point has a second point area. Once the first point area is moved for a glass distance number and is aligned with the second point area, the CCD camera inspecting equipment can obtain a thickness value of the glass substrate with a resolution value and the glass distance number. In addition, the present invention also provides a method for highly accurate and real-time photoelectric glass substrate identification.