The syntheses of dimethyl 2,2'-bithiophene-4,4'-dicarboxylate (3), dimethyl 2,2'-bithiophene-3,4'-dicarboxylate (4), and dimethyl 2,2'-bithiophene-3,3'-dicarboxylate (5) are described. Single-crystal X-ray structural analysis of these compounds shows that the thiophene rings in 3 and 4 are nearly coplanar (dihedral angle close to 0 degrees ) and they adopt the anti sulfur conformation in the solid state. Further, the structure of 4 is in agreement with our previous suggestion that there is an electrostatic stabilization of the planar structure due to attraction of the 3-carbonyl oxygen to the sulfur of the distal ring. In 5, however, the thiophene rings are nearly perpendicular (dihedral angle 75 degrees ), indicating considerable steric hindrance between the two large ester groups at the 3- and 3'-positions. Unlike compounds 3 and 4, where the thiophene rings have the sulfur atoms anti, the sulfur atoms in 5 are completely syn. This is the first instance where a bithiophene has been shown to adopt a conformation where the sulfur atoms are completely syn. The solid-state conformations of 3, 4, and 5 are in agreement with ab initio theoretical calculations on these compounds; particularly, the planar conformations of 3 and 4 reflect the previously calculated low rotation barriers of these molecules.