Psychological counseling is a highly personalized and dynamic process that requires therapists to continuously monitor emotional changes, document session insights, and maintain therapeutic continuity. In this paper, we introduce PsyCounAssist, a comprehensive AI-powered counseling assistant system specifically designed to augment psychological counseling practices. PsyCounAssist integrates multimodal emotion recognition combining speech and photoplethysmography (PPG) signals for accurate real-time affective analysis, automated structured session reporting using large language models (LLMs), and personalized AI-generated follow-up support. Deployed on Android-based tablet devices, the system demonstrates practical applicability and flexibility in real-world counseling scenarios. Experimental evaluation confirms the reliability of PPG-based emotional classification and highlights the system's potential for non-intrusive, privacy-aware emotional support. PsyCounAssist represents a novel approach to ethically and effectively integrating AI into psychological counseling workflows.