Background High-quality non-invasive imaging of the deep venous system in the thorax is challenging, but nevertheless required for diagnosis of vascular pathology as well as for patient selection and preoperative planning for endovascular procedures. Purpose To compare the diagnostic quality of Gadofosveset-enhanced thoracic magnetic resonance venography, seven consecutive patients with suspected or known disease affecting the central thoracic veins were compared to seven consecutive magnetic resonance venography using conventional gadolinium-based contrast agents. Materials and methods Diagnostic capability, defined as the ability to assess vessel patency and pathologic conditions, for the major thoracic deep venous segments was assessed by two-independent readers. Both reviewers rated the overall subjective image quality on a four-graded scale, and inter-rater variability was analyzed using unweighted and weighted Cohen's kappa values. Results Diagnostic capability was generally considerably higher in the Gadofosveset group for all examined vessel segments. The overall images quality rating was significantly higher for the Gadofosveset group with a mean rating of 2.9 and 2.7 for the two-independent readers, compared to 1.2 and 1.0 for the control croup. Inter-rater variability showed less variability for the Gadofosveset group with a quadratic-weighted Cohen's Kappa value of 0.58 compared to 0.36 for the control group. Conclusion Our results show that Gadofosveset-enhanced magnetic resonance venography of the central thoracic veins is a reliable technique in clinical routine practice that results in diagnostic images, superior to conventional gadolinium-based contrast medium.