AbstractThe creation of organic dyes with excellent high power conversion efficiency (PCE) is important for the further improvement of dye‐sensitized solar cells. We wish to describe the rapid synthesis of a 112‐membered donor‐π‐acceptor dye library by a one‐pot procedure, evaluation of PCEs, and elucidation of structure–property relationships. No obvious correlations between ε, and the η were observed, whereas the HOMO and LUMO levels of the dyes were critical for η. The dyes with a more positive EHOMO, and with an ELUMO<−0.80 V, exerted higher PCEs. The proper driving forces were crucial for a high Jsc, and it was the most important parameter for a high η. The above criteria of EHOMO and ELUMO should be useful for creating high PCE dyes; nevertheless, that was not sufficient for identifying the best combination of donor, π, and acceptor blocks. Combinatorial synthesis and evaluation was important for identifying the best dye.