Suicide is an important worldwide public health problem. The aim of this study was to characterize risk factors of suicidal behavior using a large Web-based sample. The data were collected by the Brazilian Internet Study on Temperament and Psychopathology (BRAINSTEP) from November 2010 to July 2011. Suicidal behavior was assessed by an instrument based on the Suicidal Behaviors Questionnaire. The final sample consisted of 48,569 volunteers (25.9% men) with a mean ± SD age of 30.7 ± 10.1 years. More than 60% of the sample reported having had at least a passing thought of killing themselves, and 6.8% of subjects had previously attempted suicide (64% unplanned). The demographic features with the highest risk of attempting suicide were female gender (OR = 1.82, 95% CI = 1.65 to 2.00); elementary school as highest education level completed (OR = 2.84, 95% CI = 2.48 to 3.25); being unable to work (OR = 5.32, 95% CI = 4.15 to 6.81); having no religion (OR = 2.08, 95% CI = 1.90 to 2.29); and, only for female participants, being married (OR = 1.19, 95% CI = 1.08 to 1.32) or divorced (OR = 1.66, 95% CI = 1.41 to 1.96). A family history of a suicide attempt and of a completed suicide showed the same increment in the risk of suicidal behavior. The higher the number of suicide attempts, the higher was the real intention to die (P < .05). Those who really wanted to die reported more emptiness/loneliness (OR = 1.58, 95% CI = 1.35 to 1.85), disconnection (OR = 1.54, 95% CI = 1.30 to 1.81), and hopelessness (OR = 1.74, 95% CI = 1.49 to 2.03), but their methods were not different from the methods of those who did not mean to die. This large Web survey confirmed results from previous studies on suicidal behavior and pointed out the relevance of the number of previous suicide attempts and of a positive family history, even for a noncompleted suicide, as important risk factors.