Despite showing impressive abilities, large language models (LLMs) often struggle with factual inaccuracies, i.e., ''hallucinations'', even when they hold relevant knowledge. To mitigate these hallucinations, current approaches typically necessitate high-quality human factuality annotations. In this work, we explore Self-Alignment for Factuality, where we leverage the self-evaluation capability of an LLM to provide training signals that steer the model towards factuality. Specifically, we incorporate Self-Eval, a self-evaluation component, to prompt an LLM to validate the factuality of its own generated responses solely based on its internal knowledge. Additionally, we design Self-Knowledge Tuning (SK-Tuning) to augment the LLM's self-evaluation ability by improving the model's confidence estimation and calibration. We then utilize these self-annotated responses to fine-tune the model via Direct Preference Optimization algorithm. We show that the proposed self-alignment approach substantially enhances factual accuracy over Llama family models across three key knowledge-intensive tasks on TruthfulQA and BioGEN.