Few researchers have examined how the components of the Practice Environment Scale of the Nursing Work Index (PES‐NWI) relate to nurses' well‐being at multiple organizational levels. The objective of the study was to perform a multilevel assessment of the relationships of the PES‐NWI subscales with three nurse outcomes: job satisfaction, emotional exhaustion, and turnover intentions. Additionally, we tested the multilevel factor structure of the PES‐NWI. In a sample of 699 full‐time registered nurses in 79 units and 9 branches of a hospital system, relationships of the NWI with nurse outcomes were fairly consistent across levels of analysis. However, subscales contributed differently to the three outcomes, demonstrating the complexity of environmental influences on nurses' work experience. © 2013 Wiley Periodicals, Inc. Res Nurs Health 36: 567–581, 2013