Spatiotemporal clustering of vehicle emissions, which reveals the evolution pattern of air pollution from road traffic, is a challenging representation learning task due to the lack of supervision. Some recent work building upon graph convolutional network (GCN) models the intrinsic spatiotemporal correlations among the nodes in road networks as graph representations for clustering. However, these existing methods ignore the interactions between spatial and temporal variations in vehicle emissions, resulting in incomplete descriptions and inaccurate detection of the evolution pattern of air pollution. To address this issue, this article proposes a two-way self-supervised spatiotemporal representation learning scheme, in which the temporal and spatial features are progressively learned in a mutually reinforced manner. Our proposed method is based on the observation that though the variation in vehicle emissions in the road network is consistent in the spatial and temporal domains, its expression is more distinct in temporal sequences. To this end, the input emission data are first projected into an initial temporal representation space spanned by the captured features from a pretrained BiLSTM network. Then the generated distribution of temporal features is used to construct an objective constraint for high-purity clustering through a two-way self-supervised mechanism, which is leveraged as a constraint for the feature clustering of a GCN. Furthermore, to eliminate the initial errors, a joint optimization scheme is presented to generate the decoupled clustering results through the progressive refinement of representation and clustering. Our proposed method is evaluated on the traffic emission dataset of Xian city in 2020, and the experimental results have demonstrated the superiority against the state-of-the-art.