Machine unlearning (MU) empowers individuals with the `right to be forgotten' by removing their private or sensitive information encoded in machine learning models. However, it remains uncertain whether MU can be effectively applied to Multimodal Large Language Models (MLLMs), particularly in scenarios of forgetting the leaked visual data of concepts. To overcome the challenge, we propose an efficient method, Single Image Unlearning (SIU), to unlearn the visual recognition of a concept by fine-tuning a single associated image for few steps. SIU consists of two key aspects: (i) Constructing Multifaceted fine-tuning data. We introduce four targets, based on which we construct fine-tuning data for the concepts to be forgotten; (ii) Joint training loss. To synchronously forget the visual recognition of concepts and preserve the utility of MLLMs, we fine-tune MLLMs through a novel Dual Masked KL-divergence Loss combined with Cross Entropy loss. Alongside our method, we establish MMUBench, a new benchmark for MU in MLLMs and introduce a collection of metrics for its evaluation. Experimental results on MMUBench show that SIU completely surpasses the performance of existing methods. Furthermore, we surprisingly find that SIU can avoid invasive membership inference attacks and jailbreak attacks. To the best of our knowledge, we are the first to explore MU in MLLMs. We will release the code and benchmark in the near future.