Background: An increasing amount of research indicates that positive psychological factors, such as optimism, might be beneficial for cardiovascular health. However, most studies have focused on cardiovascular events. The present study aimed to investigate associations between optimism and subclinical outcomes related to cardiovascular health. Methods: This cross-sectional study used data from SCAPIS Malmö, Sweden, including 6251 randomly selected men and women from the Malmö municipality area, aged 50 to 64 years. Optimism was assessed via the LOT-R questionnaire, but also by using the two subscales of LOT-R, assessing optimism and pessimism separately. Arterial health was assessed as the coronary artery calcium score, ankle-brachial index, and aortic augmentation index. Cardiovascular risk was estimated using the SCORE instrument. Adjustments were made for sociodemographic factors, depression, and cardiovascular risk factors. Results: Those who were most optimistic had lower odds of coronary artery calcification, with an odds ratio of 0.74 (95% confidence interval 0.58, 0.93), compared to those who were least optimistic. Also, higher levels of optimism were associated with a general pattern of lower aortic augmentation index, and with higher ankle-brachial index on both left and right side. For coronary artery calcification associations seemed to be mediated primarily through an absence of pessimism. The associations were reduced after adjustments, but persisted for measures of arterial function. Conclusions: The results indicate that optimism might be health protective with regard to arterial function, but with regard to coronary artery calcification it was rather the absence of pessimism that was of importance.