Imbalanced node classification is a critical challenge in graph learning, where most existing methods typically utilize Graph Neural Networks (GNNs) to learn node representations. These methods can be broadly categorized into the data-level and the algorithm-level. The former aims to synthesize minority-class nodes to mitigate quantity imbalance, while the latter tries to optimize the learning process to highlight minority classes. However, neither category addresses the inherently imbalanced graph structure, which is a fundamental factor that incurs majority-class dominance and minority-class assimilation in GNNs. Our theoretical analysis further supports this critical insight. Therefore, we propose GraphSB (Graph Structural Balance), a novel framework that incorporates Structural Balance as a key strategy to address the underlying imbalanced graph structure before node synthesis. Structural Balance performs a two-stage structure optimization: Structure Enhancement that adaptively builds similarity-based edges to strengthen connectivity of minority-class nodes, and Relation Diffusion that captures higher-order dependencies while amplifying signals from minority classes. Thus, GraphSB balances structural distribution before node synthesis, enabling more effective learning in GNNs. Extensive experiments demonstrate that GraphSB significantly outperforms the state-of-the-art methods. More importantly, the proposed Structural Balance can be seamlessly integrated into state-of-the-art methods as a simple plug-and-play module, increasing their accuracy by an average of 3.67\%.