Polyhedral freeform surface prism is an important optical part, and the measurement of its full profile plays a crucial role in evaluating and improving its manufacturing process. One of the most suitable methods is to combine line laser scanning with multi-degree-of-freedom motion mechanisms to perform scanning measurements on polyhedral freeform surface prisms. Currently, when using line laser for measuring polyhedral freeform surface prisms, there are issues such as insufficient system degrees of freedom, unstable S/N (signal-to-noise ratio) of the light stripe, and high accuracy requirements for the measurement path, resulting in incomplete measurement results. To address the issue of insufficient system degrees of freedom, this paper establishes a five-axis-based line laser scanning system, ensuring measurement accuracy through system calibration. For the problem of unstable S/N of the light stripe in line laser measurement of freeform prisms, this paper proposes a method to evaluate the S/N of the light stripe and confirms the curve of S/N change with view angle through experiments on the measured surface. The optimal view angles for each surface are selected from this curve to obtain light stripe curves with higher S/N. Regarding the issue of increased accuracy requirements for the measurement path due to the view angle selection, this paper proposes an iterative measurement method. By pre-cognizing the part posture, the initial measurement path and results are obtained, and the part posture is iterated continuously based on the measurement results and model information to converge to the actual posture, thus obtaining a high-precision measurement path and achieving full-profile measurement of the part. Full-profile measurements and comparative experiments on standard spheres, flat prisms, and freeform prisms were conducted. Experimental results show that the measurement accuracy of the system can reach the level of 10 µm, and the measurement repeatability can reach the sub-micrometer level. The measurement area can be expanded by about 30% after several iterations, verifying the feasibility of the proposed view angle selection method and iterative measurement method.