The evolution of Large Language Models (LLMs) has catalyzed a paradigm shift from superficial instruction following to rigorous long-horizon reasoning. While Group Relative Policy Optimization (GRPO) has emerged as a pivotal mechanism for eliciting such post-training reasoning capabilities due to its exceptional performance, it remains plagued by significant training instability and poor sample efficiency. We theoretically identify the root cause of these issues as the lack of distinctiveness within on-policy rollouts: for routine queries, highly homogeneous samples induce destructive gradient conflicts; whereas for hard queries, the scarcity of valid positive samples results in ineffective optimization. To bridge this gap, we propose Distinctiveness-aware Group Relative Policy Optimization (DaGRPO). DaGRPO incorporates two core mechanisms: (1) Sequence-level Gradient Rectification, which utilizes fine-grained scoring to dynamically mask sample pairs with low distinctiveness, thereby eradicating gradient conflicts at the source; and (2) Off-policy Data Augmentation, which introduces high-quality anchors to recover training signals for challenging tasks. Extensive experiments across 9 mathematical reasoning and out-of-distribution (OOD) generalization benchmarks demonstrate that DaGRPO significantly surpasses existing SFT, GRPO, and hybrid baselines, achieving new state-of-the-art performance (e.g., a +4.7% average accuracy gain on math benchmarks). Furthermore, in-depth analysis confirms that DaGRPO effectively mitigates gradient explosion and accelerates the emergence of long-chain reasoning capabilities.