Reinforcement learning with verifiable rewards (RLVR) has emerged as a powerful paradigm for enhancing the reasoning capabilities of large language models (LLMs). However, its effectiveness is substantially hindered by the prevalence of ineffective training data: many sampled prompts yield response groups that are either entirely correct or entirely incorrect, resulting in zero-variance rewards and limited learning signals. Recent state-of-the-art methods address this issue through extensive LLM rollouts to filter ineffective samples, but at the cost of considerable computational overhead. Alternative approaches, including predictive sampling and trajectory replay, aim to improve data efficiency but often remain insufficient and may introduce additional issues such as systematic bias or suboptimal constraints. To address these limitations, we propose Group Prioritized Off-Policy Optimization (POPO), a simple yet effective framework that fully exploits effective training batches without additional rollout overhead. POPO comprises two key components: prioritized group replay and decoupled off-policy optimization. The former replaces ineffective on-policy groups with effective off-policy groups via a recency-based replay mechanism that jointly considers sample quality and the degree of off-policiness. To further mitigate the off-policy gap, POPO employs decoupled importance sampling to correct off-policy bias while maintaining stable policy updates under consistent trust-region constraints. Empirical evaluations across diverse reasoning tasks, including mathematics, planning, and visual geometry, demonstrate that POPO substantially accelerates RL finetuning and achieves strong reasoning performance with significantly fewer rollouts.