The unbalanced structure has been one of the major problems for China’s advertising industry. The emergence of big data not only brings great challenges to advertising industry, but also provides opportunities to some extent at the same time. Specifically, the structure of advertising industry would get optimized and upgraded. Based on relevant theories of Industry Economics, this paper applies statistical analysis techniques and comparative analysis methods to study the structure optimization of advertising industry in the age of big data. The technology innovation is an important power to promote the industrial structure optimization. The Industrial structure optimization includes two aspects, the industrial structure rationalization and the industrial structure supererogation. In the age of bigBig data, the data-driven collaborative operation mechanism promotes the rationalization of the advertising industrial structure, and the advertising technology innovation caused by big data promotes the industrial structure supererogation. With the effect of the two aspects, big data makes the structure of advertising industry optimized and upgraded.