Reliability can be estimated using structural equation modeling (SEM). Two potential problems with this approach are that estimates may be unstable with small sample sizes and biased with misspecified models. A Monte Carlo study was conducted to investigate the quality of SEM estimates of reliability by themselves and relative to coefficient alpha. The SEM approach showed minimal bias when the model was correctly specified if items were relatively well defined by their underlying factor(s). They tended to demonstrate somewhat greater bias when the model was misspecified, particularly underspecified. Overall, SEM estimates were more stable than anticipated. Researchers are more likely to obtain accurate estimates of reliability using SEM by conducting large-sample studies with well-constructed scales and critically assessing model fit. (Contains 6 tables.)