The urban growth of large cities in China is at a critical stage with the booming of the economy and impressive increase of the population and traffic demand. This paper studies and qualifies the growth and accessibility of a rapid rail transit network, and characterizes the relations with urban development using a spatio-temporal modelling approach. Several measures of the network topological structure, i.e., beta index (β), cyclomatic number (μ), alpha index (α) and gamma index (γ), are selected in order to examine and quantify the overall metro network growth of the city of Guangzhou in China. The results show that the current spatial connectivity of the Guangzhou’s metro network is relatively low, this stressing the need to augment the reliability of the connections between the network nodes, and to increase the number of circuits in the network. A travel-time matrix is modelled and evaluates the nodes accessibility and characterizes the spatio-temporal evolution of the metro network. The spatial interaction between the different nodes of the network, as well as nodes accessibility are analyzed and derived from a potential-based model. The extension of the metro network clearly shows a dramatic tendency of positive accessibility evolution but with regional differences. In particular, the core of the city is surrounded by areas with highest accessibility values and gradually expanding outward from the core, while the locations of transfer stations have significant influence on the variation of network time-based accessibility. Taking into account different network development scenarios, the approach reveals regional accessibility differences in the metropolitan area of the city of Guangzhou, this clearly illustrating the impact of network accessibility in urban development.