As the field of Multimodal Large Language Models (MLLMs) continues to evolve, their potential to handle mathematical reasoning tasks is promising, as they can handle multimodal questions via cross-modal understanding capabilities compared to text-only LLMs. Current mathematical benchmarks predominantly focus on evaluating MLLMs' problem-solving ability, yet there is a crucial gap in addressing more complex scenarios such as error detection, for enhancing reasoning capability in complicated settings. To fill this gap, we formally formulate the new task — multimodal error detection, and introduce ErrorRadar, the first benchmark designed to assess MLLMs' capabilities in such a task. ErrorRadar evaluates two sub-tasks: error step identification and error categorization, providing a framework for evaluating MLLMs' complex mathematical reasoning ability. It consists of 2,500 high-quality multimodal K-12 mathematical problems, collected from real-world student interactions in an educational organization, with expert-based annotation and metadata such as problem type and error category. Through extensive experiments, we evaluated both open-source and closed-source representative MLLMs, benchmarking their performance against educational expert evaluators. Results indicate challenges still remain, as GPT-4o with best model performance is still around 10% behind human evaluation.