Objectives: Using two intensive longitudinal data sets with different timescales (90 minutes, daily), we examined emotion network density, a metric of emotional inflexibility, as a predictor of clinical-level anxiety and depression. Design: Mobile-based intensive longitudinal assessments. Methods: 119 participants (61 anxious and depressed, 58 healthy controls) completed ecological momentary assessment (EMA) to rate a variety of negative (NE) and positive emotions (PE) 9 times per day for 8 days using a mobile phone application. 169 participants (97 anxious and depressed and 72 healthy controls) completed an online daily diary on their NE and PE for 50 days. Multilevel vector autoregressive models were run to compute NE and PE network densities in each data set. Results: In the EMA data set, both NE and PE network densities significantly predicted participants’ diagnostic status above and beyond demographics and the mean and standard deviation of NE and PE. Greater NE network density and lower PE network density were associated with anxiety and depression diagnoses. In the daily diary data set, NE and PE network densities did not significantly predict the diagnostic status. Conclusions: Greater inflexibility of NE and lower inflexibility of PE, indexed by emotion network density, are potential clinical markers of anxiety and depressive disorders when assessed at intra-daily levels as opposed to daily levels. Considering emotion network density, as well as the mean level and variability of emotions in daily life, may contribute to diagnostic prediction of anxiety and depressive disorders.