We developed one-flow syntheses of unsymmetrical sulfamides and N-substituted sulfamate esters by changing a nucleophile and a tertiary amine from inexpensive and commercially available chlorosulfonic acid. In the synthesis of N-substituted sulfamate esters, unexpected symmetrical sulfite formation was suppressed by changing the tertiary amine. The effect of tertiary amines was proposed using linear regression. Our approach rapidly (≤90 s) provides desired products containing acidic and/or basic labile groups without tedious purification under mild (20 °C) conditions.