AbstractThe title triarylamine N,N‐bis(9,9‐dimethyl‐9H‐fluoren‐2‐yl)‐3′,3′,4′,7′‐tetramethyl‐2′,3′‐dihydrospiro[fluorene‐9,1′‐indene]‐2‐amine is a new hole transport material for organic solar cells. After investigating different discovery approaches (Schemes 1 + 2), a multi gram‐scale synthetic sequence was developed (Scheme 4). The key intermediate 2‐bromo‐9‐(2,5‐dimethylphenyl)‐9H‐fluorene was accessible from 2‐bromo‐9‐fluorenone by either the sequence Grignard reaction, Et3SiH/BF3 reduction or by direct arylation of the corresponding 2‐bromo‐9‐fluorenol. Alkylation at C(9) of 2‐bromo‐9‐(2,5‐dimethylphenyl)‐9H‐fluorene with methallyl chloride and cyclization by an intramolecular Friedel‐Crafts alkylation led to the key building block 2‐bromo‐3′,3′,4′,7′‐tetramethyl‐2′,3′‐dihydrospiro[fluorene‐9,1′‐indene] (Scheme 4). A Buchwald‐Hartwig coupling was employed (Scheme 3 + 4) for the assembly of the final triarylamines. The developed gram‐scale synthesis of the title compound is scalable and chromatography‐free with an overall yield >25 % over 5 steps.