The aim of this study was to determine the accuracy of sonographic chorionicity determination in the largest sample of twin pregnancies to date. We retrospectively analyzed 463 twin pregnancies delivered over a 6-year period to determine in each case what the antenatal sonographic prediction of chorionicity was, and then what the subsequent post partum pathological diagnosis of chorionicity was. Out of 436 twin pregnancies, 428 were correctly diagnosed for chorionicity as confirmed by pathology reports. Sonography as a screening tool for monochorionic twin pregnancies has a sensitivity of 100%, a specificity of 97.9% and a predictive value positive of 88.2%. Transvaginal scanning in the first trimester determined twin chorionicity with a sensitivity and a specificity of 100%. This study has confirmed in the largest sample to date that sonographic chorionicity determination is best done in the first trimester using vaginal scans, where it has 100% accuracy.