Maritime transport plays a critical role in global logistics. Compared to road transport, the pace of research and development is much slower for maritime transport. It faces many major challenges, such as busy ports, long journeys, significant accidents, and greenhouse gas emissions. The problems have been exacerbated by recent regional conflicts and increasing international shipping demands. Maritime Autonomous Surface Ships (MASSs) are widely regarded as a promising solution to addressing maritime transport problems with improved safety and efficiency. With advanced sensing and path-planning technologies, MASSs can autonomously understand environments and navigate without human intervention. However, the complex traffic and water conditions and the corner cases are large barriers in the way of MASSs being practically deployed. In this paper, to address the above issues, we investigated the application of Large Language Models (LLMs), which have demonstrated strong generalization abilities. Given the substantial computational demands of LLMs, we propose a framework for LLM-assisted navigation in connected MASSs. In this framework, LLMs are deployed onshore or in remote clouds, to facilitate navigation and provide guidance services for MASSs. Additionally, certain large oceangoing vessels can deploy LLMs locally, to obtain real-time navigation recommendations. To the best of our knowledge, this is the first attempt to apply LLMs to assist with ship navigation. Specifically, MASSs transmit assistance requests to LLMs, which then process these requests and return assistance guidance. A crucial aspect, which has not been investigated in the literature, of this safety-critical LLM-assisted guidance system is the knowledge and safety performance of the LLMs, in regard to ship handling, navigation rules, and skills. To assess LLMs’ knowledge of navigation rules and their qualifications for navigation assistance systems, we designed and conducted navigation theory tests for LLMs, which consisted of more than 1500 multiple-choice questions. These questions were similar to the official theory exams that are used to award the Officer Of the Watch (OOW) certificate based on the Standards of Training, Certification, and Watchkeeping (STCW) for Seafarers. A wide range of LLMs were tested, which included commercial ones from OpenAI and Baidu and an open-source one called ChatGLM, from Tsinghua. Our experimental results indicated that among all the tested LLMs, only GPT-4o passed the tests, with an accuracy of 86%. This suggests that, while the current LLMs possess significant potential in regard to navigation and guidance systems for connected MASSs, further improvements are needed.