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Retrieval-Augmented Generation (RAG) faces a core bottleneck with knowledge-sparse and semantically ambiguous long-tail queries, where retrieval noise distorts reasoning and necessitates costly post-processing. To tackle this, we propose RaCoT (Retrieval-aware Contrastive-of-Thought), a novel framework that shifts contrastive thinking to the pre-retrieval stage. By automatically generating a semantically adjacent yet differently answered contrastive question and extracting a Δ-Prompt to capture their key differences, RaCoT guides the model to proactively focus on the "critical details that determine answer divergence." This approach allows it to suppress semantic interference within a single retrieval pass, overcoming the theoretical bottleneck of single-vector queries that struggle to simultaneously encode signals for what to attend to and what to ignore. On six authoritative benchmarks, including PopQA and TriviaQA-unfiltered, RaCoT outperforms strong baselines like RankRAG and Self-RAG by 0.9-2.4 percentage points. It exhibits superior robustness, with a performance drop of only 8.6% in adversarial tests, far surpassing the over 15% degradation in other methods. Furthermore, its low latency (3.12s) and token overhead (11.54) place it on the accuracy-efficiency Pareto frontier, while ablation studies validate the necessity of each component. Ultimately, RaCoT reframes the RAG paradigm from "post-hoc context cleaning" to "a priori shaping of discriminative reasoning," offering an efficient and robust path toward reliable AI systems for real-time, resource-constrained deployments.