Stable diarylcarbenium salts, obtained by the direct coupling of indole or indole derivatives with aryl (or heteroaryl) aldehydes in the presence of a strong organic Brønsted acid, have been employed in the direct alkylation of aldehydes. Excellent enantiomeric excesses and good diastereomeric ratios were obtained with a number of aryl or heteroaryl(3-indolyl)carbenium ions as the highly stable o-benzenedisulfonimide (OBS) salts and with the reaction promoted by the Hayashi–Jørgensen catalyst. A one-pot, three-component, stereoselective alkylation of aldehydes affording the same compounds was also investigated with various aldehydes, indole derivatives, and organocatalysts. The results obtained with the isolated carbenium ions were superior in terms of yields and stereoselectivity.