Social network analysis (SNA) is an increasingly popular and effective tool for modeling psychological phenomena. Through application to the personality literature, social networks, in conjunction with passive, non-invasive sensing technologies, have begun to offer powerful insight into personality state variability. Resultant constructions of social networks can be utilized alongside machine learning-based frameworks to uniquely model personality states. Accordingly, this work leverages data from a previously published study to combine passively collected wearable sensor information on face-to-face, workplace social interactions with ecological momentary assessments of personality state. Data from 54 individuals across six weeks was used to explore the relative importance of 26 unique structural and nodal social network features in predicting individual changes in each of the Big Five (5F) personality states. Changes in personality state were operationalized by calculating the weekly root mean square of successive differences (RMSSD) in 5F state scores measured daily via self-report. Using only SNA-derived features from wearable sensor data, boosted tree-based machine learning models explained, on average, approximately 28–30% of the variance in individual personality state change. Model introspection implicated egocentric features as the most influential predictors across 5F-specific models, with network efficiency, constraint, and effective size measures among the most important. Feature importance profiles for each 5F model partially echoed previous empirical findings. Results support future efforts focusing on egocentric components of SNA and suggest particular investment in exploring efficiency measures to model personality fluctuations within the workplace setting.