Leveraging mathematical Large Language Models (LLMs) for proof generation is a fundamental topic in LLMs research. We argue that the ability of current LLMs to prove statements largely depends on whether they have encountered the relevant proof process during training. This reliance limits their deeper understanding of mathematical theorems and related concepts. Inspired by the pedagogical method of "proof by counterexamples" commonly used in human mathematics education, our work aims to enhance LLMs' ability to conduct mathematical reasoning and proof through counterexamples. Specifically, we manually create a high-quality, university-level mathematical benchmark, CounterMATH, which requires LLMs to prove mathematical statements by providing counterexamples, thereby assessing their grasp of mathematical concepts. Additionally, we develop a data engineering framework to automatically obtain training data for further model improvement. Extensive experiments and detailed analyses demonstrate that CounterMATH is challenging, indicating that LLMs, such as OpenAI o1, have insufficient counterexample-driven proof capabilities. Moreover, our exploration into model training reveals that strengthening LLMs' counterexample-driven conceptual reasoning abilities is crucial for improving their overall mathematical capabilities. We believe that our work offers new perspectives on the community of mathematical LLMs.