Reflection removal is challenging due to complex light interactions, where reflections obscure important details and hinder scene understanding. Polarization naturally provides a powerful cue to distinguish between reflected and transmitted light, enabling more accurate reflection removal. However, existing methods often rely on small-scale or synthetic datasets, which fail to capture the diversity and complexity of real-world scenarios. To this end, we construct a large-scale dataset, PolarRR, for polarization-based reflection removal, which enables us to train models that generalize effectively across a wide range of real-world scenarios. The PolarRR dataset contains 6,500 well-aligned mixed-transmission image pairs, 8x larger than existing polarization datasets, and is the first to include both RGB and polarization images captured across diverse indoor and outdoor environments with varying lighting conditions. Besides, to fully exploit the potential of polarization cues for reflection removal, we introduce PolarFree, which leverages diffusion process to generate reflection-free cues for accurate reflection removal. Extensive experiments show that PolarFree significantly enhances image clarity in difficult reflective scenarios, setting a new benchmark for polarized imaging and reflection removal. Code and dataset will be public after acceptance.