Large Language Models (LLMs) have achieved remarkable success across various domains. However, a fundamental question remains: Can LLMs effectively utilize causal knowledge for prediction and generation? Through empirical studies, we find that LLMs trained directly on large-scale data often capture spurious correlations rather than true causal relationships, leading to suboptimal performance, especially in out-of-distribution (OOD) scenarios. To address this challenge, we propose Causal Attention Tuning (CAT), a novel approach that injects fine-grained causal knowledge into the attention mechanism. We propose an automated pipeline that leverages human priors to automatically generate token-level causal signals and introduce the Re-Attention mechanism to guide training, helping the model focus on causal structures while mitigating noise and biases in attention scores. Experimental results on our proposed Spurious Token Game (STG) benchmark and multiple downstream tasks demonstrate that our approach effectively leverages causal knowledge for prediction and remains robust in OOD scenarios. The CAT achieves an average improvement of 5.76% on the STG dataset and 1.56% on downstream tasks. Notably, the OOD performance of the Llama-3.1-8B model on STG_M increased from 64.5% to 90.5%, and Qwen's OOD performance on the STG_H dataset improved from 25.4% to 55.9%. Implementation details can be found at https://github.com/Kairong-Han/CAT.