The impact of the organic species in the synthetic gel of ZSM-5 on the distribution of Al atoms in the MFI framework and catalytic performance was investigated; ZSM-5 zeolites were synthesized by exclusively using TPAOH, and Na cations with PET to elucidate how the distribution of Al atoms is governed by the types of organic species in the synthetic gel. The distribution of Al atoms was investigated by Al-27 MAS NMR technique and constrain index (CI). Catalytic cracking of 1-octene over the ZSM-5 catalysts was carried out to estimate "hydrogen transfer coefficient (HTC) and cracking mechanism ratio (CMR) values". We found that HTC and CMR values are dependent on the distribution of Al atoms. The fine-control of Al distribution in the MFI structure could improve the tolerance for coke deposition in 1-octene cracking.