The period after psychiatric hospitalization is an extraordinarily high‐risk period for suicidal thoughts and behaviours (STBs). Affective–cognitive constructs (ACCs) are salient risk factors for STBs, and intensive longitudinal metrics of these constructs may improve personalized risk detection and intervention. However, limited research has examined how within‐person daily levels and between‐person dynamic metrics of ACCs relate to STBs after hospital discharge. Adult psychiatric inpatients (N = 95) completed a 65‐day ecological momentary assessment protocol after discharge as part of a 6‐month follow‐up period. Using dynamic structural equation models, we examined both within‐person daily levels and between‐person dynamic metrics (intensity, variability and inertia) of positive and negative affect, rumination, distress intolerance and emotion dysregulation as risk factors for STBs. Within‐person lower daily levels of positive affect and higher daily levels of negative affect, rumination, distress intolerance and emotion dysregulation were risk factors for next‐day suicidal ideation (SI). Same‐day within‐person higher rumination and negative affect were also risk factors for same‐day SI. At the between‐person level, higher overall positive affect was protective against active SI and suicidal behaviour over the 6‐month follow‐up, while greater variability of rumination and distress intolerance increased risk for active SI, suicidal behaviour and suicide attempt. The present study provides the most comprehensive examination to date of intensive longitudinal metrics of ACCs as risk factors for STBs. Results support the continued use of intensive longitudinal methods to improve STB risk detection. Interventions focusing on rumination and distress intolerance may specifically help to prevent suicidal crises during critical transitions in care.