Patients presenting to the emergency department with acute chest pain, negative conventional troponin and electrocardiogram require serial testing to rule out acute coronary syndrome (ACS). We studied the association of highly sensitive troponin (hsTn) I with vulnerable plaque features as detected by coronary dual source computed tomography angiography (DSCTA) and determined whether hsTn I at the time of presentation combined with early DSCTA could improve classification of patients as high-risk or low risk for ACS. We included 220 patients with acute chest pain, negative electrocardiogram and conventional troponin who underwent DSCTA and had hsTn I measured at the time of presentation. The patients were categorized as having hsTn I below the limit of detection (low risk), intermediate and above the 99th percentile (high risk). Readers assessed DSCTA qualitatively for the presence of significant CAD (≥50% stenosis), calcified and non-calcified coronary plaque, and vulnerable plaque features (positive remodeling, low CT attenuation plaque, napkin-ring sign, spotty calcium). The mean age of the population was 50.3 ± 8.2 years (43% women). ACS during the index hospitalization occurred in 36 (16.3%) patients (myocardial infarction n = 8, unstable angina pectoris n = 28). HsTn I was below the limit of detection, intermediate, and above 99th percentile in 39 (17.7%), 139 (86.9%), and 42 (19.1%) patients, respectively. Across the categories of low risk, intermediate and high risk of hsTn I, there was increase in prevalence of ≥50% stenosis (0, 11.5, and 61.9% of patients; p < 0.001), any plaque (35.9, 51.1, and 85.7% of patients; p < 0.001) and high-risk plaque (0, 36.0, and 85.7% of patients; p < 0.001). None of the patients in low risk HsTn I group had ACS. ACS occurred in 10.1% of the intermediate hsTn I group and in 52.3% of the patients with high risk hsTnI group. Severity of stenosis and presence of vunerable plaque as detected by DSCTA are associated with increasing levels of hsTn I. DSCTA at the time of presentation with the assessment for both stenosis and high-risk plaque improved the diagnostic accuracy for ACS in the intermediate hsTn I group patients.