Affordance theory suggests that environments inherently provide action possibilities shaping perception and behavior. While Multimodal Large Language Models (MLLMs) achieve strong performance in vision-language tasks, their ability to perceive affordance, which is crucial for intuitive and safe interactions, remains underexplored. To address this, we introduce **A4Bench**, a novel benchmark designed to evaluate the affordance perception abilities of MLLMs across two dimensions: 1) Constitutive Affordance, assessing understanding of inherent object properties through 1,282 questionanswer pairs spanning nine sub-disciplines, and 2) Transformative Affordance, probing dynamic and contextual nuances (e.g., misleading, time-dependent, cultural, or individual-specific affordance) with 718 challenging question-answer pairs. We evaluate 17 MLLMs (nine proprietary and eight open-source) and compare them to human performance. Results show that proprietary models generally outperform open-source ones, yet all models perform far below humans, especially in transformative affordance. Furthermore, even top-performing models, such as Gemini-2.0-Pro (18.05% overall exact match accuracy), significantly lag behind human performance (best: 85.34%, worst: 81.25%). These findings highlight critical gaps in environmental understanding of MLLMs and provide a foundation for advancing AI systems toward more robust, context-aware interactions.