A proline-squaraine ligand (Pro-SqEB) that demonstrates high levels of stereoselectivity in olefin cyclopropanations when anchored to a Rh2II scaffold is introduced. High yields and enantioselectivities were achieved in the cyclopropanation of alkenes with diazo compounds in the presence of Rh2(Pro-SqEB)4. Notably, the unique electronic and steric design of this catalyst enabled the use of polar solvents that are otherwise incompatible with most RhII complexes.