Attributed graphs, which contain rich contextual features beyond just network structure, are ubiquitous and have been observed to benefit various network analytics applications. Graph structure optimization, aiming to find the optimal graphs in terms of some specific measures, has become an effective computational tool in complex network analysis. However, traditional model-free methods suffer from the expensive computational cost of evaluating graphs; existing vectorial Bayesian optimization methods cannot be directly applied to attributed graphs and have the scalability issue due to the use of Gaussian processes (GPs). To bridge the gap, in this paper, we propose a novel scalable Deep Graph Bayesian Optimization (DGBO) method on attributed graphs. The proposed DGBO prevents the cubical complexity of the GPs by adopting a deep graph neural network to surrogate black-box functions, and can scale linearly with the number of observations. Intensive experiments are conducted on both artificial and real-world problems, including molecular discovery and urban road network design, and demonstrate the effectiveness of the DGBO compared with the state-of-the-art.