Everyday speech conveys far more than words, it reflects who we are, how we feel, and the circumstances surrounding our interactions. Yet, most existing speech datasets are acted, limited in scale, and fail to capture the expressive richness of real-life communication. With the rise of large neural networks, several large-scale speech corpora have emerged and been widely adopted across various speech processing tasks. However, the field of voice conversion (VC) still lacks large-scale, expressive, and real-life speech resources suitable for modeling natural prosody and emotion. To fill this gap, we release NaturalVoices (NV), the first large-scale spontaneous podcast dataset specifically designed for emotion-aware voice conversion. It comprises 5,049 hours of spontaneous podcast recordings with automatic annotations for emotion (categorical and attribute-based), speech quality, transcripts, speaker identity, and sound events. The dataset captures expressive emotional variation across thousands of speakers, diverse topics, and natural speaking styles. We also provide an open-source pipeline with modular annotation tools and flexible filtering, enabling researchers to construct customized subsets for a wide range of VC tasks. Experiments demonstrate that NaturalVoices supports the development of robust and generalizable VC models capable of producing natural, expressive speech, while revealing limitations of current architectures when applied to large-scale spontaneous data. These results suggest that NaturalVoices is both a valuable resource and a challenging benchmark for advancing the field of voice conversion. Dataset is available at: https://huggingface.co/JHU-SmileLab