As for vision-based pose estimation, which is also known as the PnP problem, non-iterative algorithms are more efficient. Precise extraction of 2D projections of feature points is important. If the projections of the feature points are not accurately extracted, the pose estimation accuracy is reduced. Under the condition of natural light, a camera captures the images of feature points, and the existence of high-light regions in the image affects the extraction accuracy of 2D projections of feature points, which reduces the number of effective feature points and leads to poor pose estimation accuracy. In the redundant cases (n > 4), redundant feature points are introduced as additional information, increasing the number of effective feature points to reduce the impact of high-light regions and improve the pose estimation accuracy. For the non-redundant cases (n = 4), it was difficult to ensure pose estimation accuracy. To solve this problem, a non-iterative pose estimation method based on the optimum polarization angle via four corner points of a parallelogram was proposed in this study. First, a model for solving optimum polarization angle was established. Thereafter, on the premise of the optimum polarization angle, the images were captured. Finally, the projections of the four corner points of a parallelogram were extracted, and the object pose was solved non-iteratively according to the four corner points. The corner point extraction experimental results show that the slope difference between the two parallel sides of each parallelogram under the condition of optimum polarization angle is less than that under the condition of natural light, thereby proving the improvement of the imaging quality. Measurement accuracy verification experiments prove that our pose estimation algorithm and the optimum polarization angle is the best combination to improve the non-iterative pose estimation accuracy in non-redundant cases. In the measurement range of −60-+60°, the angle measurement error was less than ±0.0491°. In the measurement range of 0–20 mm, the displacement measurement error was less than ±0.0435 mm.