The concept is not entirely a sham. The formal name is "Bioavailability". It doesn't matter how much of a vitamin is present in a pill, when it isn't used by the body. Yet the label lists what's present in the pill.
However, evolution has made us quite efficient in getting vitamins from food, where they're relatively unavailable because they're locked up inside cells. It would take malice to make pure vitamin C not bio-available. It's a very simple molecule. Vitamin B12 is notorious, on the other hand. It must be actively extracted by your intestines. In that case, pills are still not a good idea: B12 availability is capped per meal. A high peak (i.e. from a pill) wouldn't be absorbed (low bio-availability) because your body doesn't have the capacity to deal with the excess.