Language model alignment methods, such as reinforcement learning from human feedback (RLHF), have led to impressive advances in language model capabilities, but existing techniques are limited by a widely observed phenomenon known as overoptimization, where the quality of the language model plateaus or degrades over the course of the alignment process. Overoptimization is often attributed to overfitting to an inaccurate reward model, and while it can be mitigated through online data collection, this is infeasible in many settings. This raises a fundamental question: Do existing offline alignment algorithms make the most of the data they have, or can their sample-efficiency be improved further? We address this question with a new algorithm for offline alignment, $\chi^2$-Preference Optimization ($\chi$PO). $\chi$PO is a one-line change to Direct Preference Optimization (DPO; Rafailov et al., 2023), which only involves modifying the logarithmic link function in the DPO objective. Despite this minimal change, $\chi$PO implicitly implements the principle of pessimism in the face of uncertainty via regularization with the $\chi^2$-divergence -- which quantifies uncertainty more effectively than KL-regularization -- and provably alleviates overoptimization, achieving sample-complexity guarantees based on single-policy concentrability -- the gold standard in offline reinforcement learning. $\chi$PO's simplicity and strong guarantees make it the first practical and general-purpose offline alignment algorithm that is provably robust to overoptimization.