Despite advances in Preference Alignment (PA) for Large Language Models (LLMs), mainstream methods like Reinforcement Learning with Human Feedback (RLHF) face notable challenges. These approaches require high-quality datasets of positive preference examples, which are costly to obtain and computationally intensive due to training instability, limiting their use in low-resource scenarios. LLM unlearning technique presents a promising alternative, by directly removing the influence of negative examples. However, current research has primarily focused on empirical validation, lacking systematic quantitative analysis. To bridge this gap, we propose a framework to explore the relationship between PA and LLM unlearning. Specifically, we introduce a bi-level optimization-based method to quantify the impact of unlearning specific negative examples on PA performance. Our analysis reveals that not all negative examples contribute equally to alignment improvement when unlearned, and the effect varies significantly across examples. Building on this insight, we pose a crucial question: how can we optimally select and weight negative examples for unlearning to maximize PA performance? To answer this, we propose a framework called Unlearning to Align (U2A), which leverages bi-level optimization to efficiently select and unlearn examples for optimal PA performance. We validate the proposed method through extensive experiments, with results confirming its effectiveness.