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This paper introduces PaZO, a preconditioned accelerated zeroth-order optimization algorithm for fine-tuning large language models (LLMs). First, we theoretically demonstrate the necessity of preconditioning in zeroth-order optimization, proving that zeroth-order stochastic gradient descent (ZO-SGD) alone fails to achieve the ideal convergence rate. Building on this, we propose a Preconditioned Simultaneous Perturbation Stochastic Approximation (PSPSA) and theoretical version of PaZO, and demonstrate that setting the order of preconditioner as $-1/2$ in PSPSA yields the improved convergence rate for PaZO. Moreover, we design a practical version of PaZO that stabilizes training via diagonal Hessian estimate and moving average technique. Extensive experiments on diverse downstream tasks with models like RoBERTa-large and OPT show PaZO’s effectiveness. Compared to other zeroth-order baselines, PaZO achieves better performance across models and tasks.