Large language models (LLMs) are increasingly deployed in domains where errors carry high social, scientific, or safety costs. Yet standard confidence estimators, such as token likelihood, semantic similarity and multi-sample consistency, remain brittle under distribution shift, domain-specialised text, and compute limits. In this work, we present Structural Confidence, a single-pass, model-agnostic framework that enhances output correctness prediction based on multi-scale structural signals derived from a model's final-layer hidden-state trajectory. By combining spectral, local-variation, and global shape descriptors, our method captures internal stability patterns that are missed by probabilities and sentence embeddings. We conduct extensive, cross-domain evaluation across four heterogeneous benchmarks-FEVER (fact verification), SciFact (scientific claims), WikiBio-hallucination (biographical consistency), and TruthfulQA (truthfulness-oriented QA). Our Structural Confidence framework demonstrates strong performance compared with established baselines in terms of AUROC and AUPR. More importantly, unlike sampling-based consistency methods which require multiple stochastic generations and an auxiliary model, our approach uses a single deterministic forward pass, offering a practical basis for efficient, robust post-hoc confidence estimation in socially impactful, resource-constrained LLM applications.