Recent advancements in Large Language Models (LLMs) demonstrate remarkable capabilities across various fields. These developments have led to more direct communication between humans and LLMs in various situations, such as social companionship and psychological support. However, LLMs often exhibit limitations in emotional perception and social competence during real-world conversations. These limitations partly originate from their inability to adapt their communication style and emotional expression to different social and task contexts. In this work, we introduce PersonaFuse, a novel LLM post-training framework that enables LLMs to adapt and express different personalities for varying situations. Inspired by Trait Activation Theory and the Big Five personality model, PersonaFuse employs a Mixture-of-Expert architecture that combines persona adapters with a dynamic routing network, enabling contextual trait expression. Experimental results show that PersonaFuse substantially outperforms baseline models across multiple dimensions of social-emotional intelligence. Importantly, these gains are achieved without sacrificing general reasoning ability or model safety, which remain common limitations of direct prompting and supervised fine-tuning approaches. PersonaFuse also delivers consistent improvements in downstream human-centered applications, such as mental health counseling and review-based customer service. Finally, human preference evaluations against leading LLMs, including GPT-4o and DeepSeek, demonstrate that PersonaFuse achieves competitive response quality despite its comparatively smaller model size. These findings demonstrate that PersonaFuse~offers a theoretically grounded and practical approach for developing social-emotional enhanced LLMs, marking a significant advancement toward more human-centric AI systems.