Large Language Models (LLMs) have demonstrated impressive capabilities in role-playing conversations and providing emotional support as separate research directions. However, there remains a significant research gap in combining these capabilities to enable emotionally supportive interactions with virtual characters. To address this research gap, we focus on anime characters as a case study because of their well-defined personalities and large fan bases. This choice enables us to effectively evaluate how well LLMs can provide emotional support while maintaining specific character traits. We introduce ChatAnime, the first Emotionally Supportive Role-Playing (ESRP) dataset. We first thoughtfully select 20 top-tier characters from popular anime communities and design 60 emotion-centric real-world scenario questions. Then, we execute a nationwide selection process to identify 40 Chinese anime enthusiasts with profound knowledge of specific characters and extensive experience in role-playing. Next, we systematically collect two rounds of dialogue data from 10 LLMs and these 40 Chinese anime enthusiasts. To evaluate the ESRP performance of LLMs, we design a user experience-oriented evaluation system featuring 9 fine-grained metrics across three dimensions: basic dialogue, role-playing and emotional support, along with an overall metric for response diversity. In total, the dataset comprises 2,400 human-written and 24,000 LLM-generated answers, supported by over 132,000 human annotations. Experimental results show that top-performing LLMs surpass human fans in role-playing and emotional support, while humans still lead in response diversity. We hope this work can provide valuable resources and insights for future research on optimizing LLMs in ESRP. Our datasets are available at https://github.com/LanlanQiu/ChatAnime.