With the rapid advancement of Industry 4.0 and smart manufacturing, the security of industrial control systems (ICS) has become a critical concern. As the core communication mechanisms of ICS, industrial control protocols are essential for maintaining system stability and protecting data. However, many industrial control protocols lack sufficient network security considerations in their design, making the systems vulnerable to cyberattacks such as malicious software and denial of service, which may endanger corporate interests and even national security. This paper provided a comprehensive review of the security landscape, major challenges, and development trends of industrial control protocols. Firstly, the basic concepts and classifications of industrial control protocols were introduced, and their security characteristics and vulnerabilities were analyzed. Subsequently, the application of symbolic execution, reverse analysis, and fuzz testing in vulnerability mining was discussed in detail. These technologies were particularly effective when dealing with complex industrial protocols. The paper also examined security measures such as encryption, authentication, intrusion detection, and layered defenses. Finally, it explored the application of generative large language models in ICS security, focusing on code generation, network protection, and automation control. These advancements enable ICS to transition from passive defense to proactive protection strategies. Through this research, we aim to enhance the understanding of the security challenges in industrial control protocols and provide practical solutions to improve the reliability and safety of ICS, thereby effectively safeguarding critical infrastructure from potential threats and attacks.