3 ways they can be tested:
Temperature, once up to operating temp, if it is at least 10% hotter at the rear it is working.
Flow, drill two holes, one before and one after the cat, fit a pressure guage, there should be no noticeble difference between pre and post cat readings at about 1500rpm.
Emissions test, hook it up to a probe and see if the emissions are within the range specified for that model.
By far the easiest is the temperature test. A laser thermometer is the easiest, take the car for a hard 5 minute drive, hold the revs to 2500rpm, measure in front of the cat as close to the cat body as you can, then measure after the cat the same distance from the body as the front. If it reads higher at the rear, it's working, if it is the same, it's not, if it is higher at the front, it's blocked.