When studying architectural experience in the lab, it is of paramount importance to use a proxy as close to real-world experience as possible. Whilst still images visually describe real spaces, and virtual reality allows for dynamic movement, each medium lacks the alternative attribute. To merge these benefits, we created and validated a novel dataset of valenced videos of first-person-view travel through built environments. This dataset was then used to clarify the relationship of core affect (valence and arousal) and architectural experience. Specifically, we verified the relationship between valence and fascination, coherence, and hominess - three key psychological dimensions of architectural experience which have previously been shown to explain aesthetic ratings of built environments. We also found that arousal is only significantly correlated with fascination, and that both are embedded in a relationship with spatial complexity and unusualness. These results help to clarify the nature of fascination, and to distinguish it from coherence and hominess when it comes to core affect. Moreover, these results demonstrate the utility of a video dataset of affect-laden spaces for understanding architectural experience.