While Reinforcement Learning from Human Feedback (RLHF) has become the predominant method for controlling language model outputs, it suffers from high computational costs and training instability. Guided decoding, especially value-guided methods, offers a cost-effective alternative by controlling outputs without re-training models. However, the accuracy of the value function is crucial for value-guided decoding, as inaccuracies can lead to suboptimal decision-making and degraded performance. Existing methods struggle with accurately estimating the optimal value function, leading to less effective control. We propose Iterative Value Function Optimization, a novel framework that addresses these limitations through two key components: Monte Carlo Value Estimation, which reduces estimation variance by exploring diverse trajectories, and Iterative On-Policy Optimization, which progressively improves value estimation through collecting trajectories from value-guided policies. Extensive experiments on text summarization, multi-turn dialogue, and instruction following demonstrate the effectiveness of value-guided decoding approaches in aligning language models. These approaches not only achieve alignment but also significantly reduce computational costs by leveraging principled value function optimization for efficient and effective control.