Aiming to inverstigate the effect of surface potential barrier on electron escape probability of negative electron affinity GaN photocathode, the electron escape probability is calculated by using the Boltzmann distribution and the method of transfer matrix based on Airy function. It is found that barrier I is a key influencing factor of electron escape probability, while barrier II has a limited influence. The activation photocurrent curve of the transmission-mode GaN photocathode is measured by using our built activation and evaluation experimental system of NEA GaN photocathode. The obvious increase of electron escape probability can be achieved mainly by activating Cs only. The increase of electron escape probability is not large in Cs/O activation process with only Cs activated sufficiently. The theoretical calculations are in good agreement with the photocurrent curves from experimental test. The reason is that the contribution of activating only Cs to the reducing of vacuum level for obtaining NEA state is much larger than that of activating Cs/O.