To meet the spatial perception requirements for autonomous ship navigation in common scenarios such as ocean navigation, port entry and exit, and lock passage, commercial vehicle-mounted LiDAR technology falls short of demands in aspects such as sensing distance, field of view, angular resolution, and spatial sampling density. This paper proposes a hundred-beam-scale LiDAR scheme based on large-field-of-view diffractive beam splitting and a fiber array for echo reception and presents an in-depth investigation of the angular nonuniformity of diffractive beam splitting and the microradian-scale alignment for such hundred-beam-scale large-field-of-view LiDAR. This paper considers a combination of split-beam transmission based on a high-order diffractive optical element (DOE) and echo reception based on a high-precision fiber-optic line array. The nonlinear angular characteristics of the DOE are deduced and analyzed for a large field of view. The units of the receiving fiber-optic array are designed to offset the influence of the angular nonlinearity of the DOE, ensuring high-precision receiver–transmitter alignment of the hundred-beam-scale LiDAR for beams at any order of diffraction and helping to reduce system errors. The above-described LiDAR system has undergone laboratory testing and practical engineering verification, and it provides a new optical solution for LiDAR systems at the hundred-beam scale with a large field of view, a small divergence angle, and high sampling density. The presented system achieves a registration accuracy of 66.5 μrad with 128 beams and a 10-degree field of view, greatly improving signal reception efficiency. Such LiDAR systems have a wide range of applications, including space docking, target identification, lunar and planetary exploration, and ground-based vehicle-mounted LiDAR.