Background: Worldwide thrombolysis rates remain suboptimal. Ambulance transfer is associated with greater use of this time-dependent treatment. Information on public awareness of stroke symptoms is important for planning effective education programs to promote calling of emergency services for suspected stroke. However, there is a paucity of data on this subject in European countries. Our objectives were to explore the recognition of stroke symptoms, awareness of the need to activate the emergency medical services for acute stroke events, and the association between knowledge of warning symptoms and intent to call for an ambulance among a sample representative of the adult population of Spain. This is the largest study on this subject to date in Europe. Methods: The data were taken from the Study on Nutrition and Cardiovascular Risk in Spain, a cross-sectional study conducted in a sample representative of the Spanish noninstitutionalized population aged ≥18 years in 2008–2010. Study participants were selected by multistage clustered random sampling. The households within each section were selected by random telephone dialing using the landline telephone directory as the sampling frame. Subjects in the households were selected proportionally to the distribution of the population of Spain by sex and age. The study included a computer-assisted telephone interview on stroke symptom knowledge and the first action to perform in a stroke event, based on the American Heart Association and American Stroke Association recommendations, and two home visits to perform a physical examination and to obtain blood samples. Results: Among 11,827 adults, 7,711 (65.2%; 95% CI = 64.1–66.3) identified 4–6 stroke warning symptoms, considered as adequate knowledge. A total of 1,348 (11.4%) were unable to classify any of the symptoms correctly. In the multivariate analysis, higher education was significantly associated with better knowledge of symptoms, and age ≥65 years, fair/poor self-rated health, history of obesity and known diabetes were significantly associated with less knowledge of stroke symptoms. One in 5 individuals indicated they would do something other than calling for an ambulance if they thought someone was having a stroke. The number of specific stroke warning symptoms known was directly associated with the intent to call an ambulance in a stroke event (OR adjusted for sociodemographic and clinical variables = 1.06 per symptom, 95% CI = 1.03–1.09; p < 0.001). Conclusions: In this population-based study, stroke symptom knowledge was suboptimal and only modestly associated with the intent to call for an ambulance. Educational interventions are needed to link stroke recognition more strongly to an immediate need to call for an ambulance in order to increase stroke patients’ access to thrombolysis.