Large language models (LLMs) have taken a great step towards AGI. Meanwhile, an increasing number of domain-specific problems such as math and programming boost these general-purpose models to continuously evolve via learning deeper expertise. Now is thus the time further to extend the diversity of specialized applications for knowledgeable LLMs, though collecting high quality data with unexpected and informative tasks is challenging. In this paper, we propose to use advertisement (ad) videos as a challenging test-bed to probe the ability of LLMs in perceiving beyond the objective physical content of the common visual domain. Our motivation is to take full advantage of the clue-rich and information-dense ad videos' traits, e.g., marketing logic, persuasive strategies, and audience engagement. Our contribution is three-fold, (1) To our knowledge, this is the first attempt to use ad videos with well-designed tasks to evaluate LLMs. We contribute AdsQA, a challenging ad Video QA benchmark derived from 1,544 ad videos with 10,962 clips, totaling 21.1 hours, providing 5 challenging tasks. (2) We propose ReAd-R, a Deepseek-R1 styled RL model that reflects on questions, and generates answers via reward-driven optimization. (3) We benchmark 14 top-tier LLMs on AdsQA, and our ReAd-R achieves the state-of-the-art outperforming strong competitors equipped with long-chain reasoning capabilities (e.g., VOT, and MCTSr) by a clear margin.