The geography over which maritime transportation operates is unique, combining physical, strategic, and commercial imperatives. Physical issues are stable across time, but strategic, especially commercial, considerations continually shift with the ebb and flow of the globalization process. Contextually, the distance that isolates different locations in many cases plays a vital function in these interactions. Distance is the primary element that affects the values of interaction intensities. In fact, the issue is how the intensities were reduced with distance since this reduction is generally not linear. In this regard, this article intends to pursue the issues of the shape and parameters of the distance–decay functions based on the travel time value between islands. In this regard, almost all the Azores Islands were used as a case study. The study results show that the distance–decay functions established the unique dominance of Faial Island, Pico Island, and São Jorge Island, all in the Azores central group; in addition, there was an increase in the number of passengers in those. Moreover, the dominant position is the central islands, and their coexistence with others in the environment makes them more accessible than other islands, showing Terceira Island as a potential maritime passengers’ hub in the Azores. So, with this study, it becomes clear which are the main accessibility issues within the Azores archipelago as well as efficiency should be promoted through the design of policies in maritime passengers’ transportation.