Despite the success of large language models (LLMs) in natural language generation, much evidence shows that LLMs may produce incorrect or nonsensical text. This limitation highlights the importance of discerning when to trust LLMs, especially in safety-critical domains. Existing methods, which rely on verbalizing confidence to tell the reliability by inducing top-k responses and sampling-aggregating multiple responses, often fail, due to the lack of objective guidance of confidence. To address this, we propose CONfidence-Quality-ORDerpreserving alignment approach (CONQORD), leveraging reinforcement learning with a tailored dual-component reward function. This function encompasses quality reward and orderpreserving alignment reward functions. Specifically, the order-preserving reward incentivizes the model to verbalize greater confidence for responses of higher quality to align the order of confidence and quality. Experiments demonstrate that our CONQORD significantly improves the alignment performance between confidence levels and response accuracy, without causing the model to become over-cautious. Furthermore, the aligned confidence provided by CONQORD informs when to trust LLMs, and acts as a determinant for initiating the retrieval process of external knowledge. Aligning confidence with response quality ensures more transparent and reliable responses, providing better trustworthiness.