Individuals who identify as lesbian, gay, bisexual, transgender, or queer (LGBTQ) are at a higher risk for suicidality compared to the general population. A growing body of research has investigated this risk, particularly with attention to systemic factors such as discrimination and harassment. Unfortunately, research has only examined the impact of direct discrimination on suicidality and has neglected to examine how ambient discrimination (i.e., witnessing or being made aware of discriminatory behaviors directed at someone other than yourself in your group) relates to suicidality. Additionally, although some links exist between discrimination and suicidality, the mechanisms by which these are related are understudied. This study aimed to address these gaps by exploring the effect of ambient discrimination on suicidal ideation and examining psychological pain as a mediator in this relationship. Data were collected from a sample of 200 LGBTQ-identified individuals (M age = 35 years; 53.5% female; 86% White). Results of independent t tests and a one-way multivariate ANOVA revealed greater vulnerability for ambient/direct discrimination and psychache among individuals identifying as transgender, queer, and other. Regression and mediation analyses revealed that while both ambient and direct discrimination predicted suicidal ideation, only direct discrimination accounted for unique variance in the outcome; however, both ambient and direct discrimination contributed unique variance to psychological pain, which fully mediated their relationships to suicidal ideation. Results of this study may begin to provide insight into the pathways of risk and points of intervention for suicidality in the LGBTQ community.