Accurate measurement of HIV-related stigma is key in understanding and reducing stigma for people living with HIV (PLWH). Experience sampling method (ESM) measures "state"-level phenomena and may improve understanding of daily stigma experiences of PLWH. In 109 men living with HIV, we examined: 1) associations between questionnaire (Q) and ESM internalized and enacted stigma measures; 2) psychosocial predictors (e.g., coping style, perceived HIV community stigma, helplessness) of discrepancies between Q and ESM internalized and enacted stigma; 3) whether Q or ESM measures better predict HIV outcomes. Hierarchical Linear Modeling showed moderate associations between ESM and Q measures of both internalized and enacted stigma. A majority of the psychosocial measures were associated with larger differences between both Q- and ESM-internalized stigma and enacted stigma, respectively. ESM measures were stronger predictors of visit adherence than Q measures. ESM may be advantageous in understanding moment-to-moment changes in stigma and associated processes in PLWH, particularly those with maladaptive psychological traits.