A series of alkyl‐group‐functionalized, aniline‐ and indoline‐donor‐based, unsymmetrical visible‐light‐active squaraine dyes, AM1‐3, were designed and synthesized. Dye‐sensitized solar cell (DSSC) devices were fabricated with both I−/I3− and [Cu(tmby)2]+/2+ electrolytes. DSSC devices sensitized with the AM1 and AM2 dyes showed relatively high‐power conversion efficiency of 7.44 % and 7.22 %, respectively with I−/I3− in the absence of chenodeoxycholic acid (CDCA) than those of the AM3 dye (5.41 %). The [Cu(tmby)2]+/2+ electrolyte along with poly(3,4‐ethylenedioxythiophene) (PEDOT) as cathode material showed excellent open‐circuit potentials (VOC) of 1030, 1025, and 1001 mV with the DSSC efficiency of 8.05 %, 7.96 %, and 5.84 %, respectively, for the AM1, AM2, and AM3 dyes in the absence of CDCA. Here, the AM1 dye exhibited the maximum DSSC efficiency of 8.05 % and VOC of 1030 mV, which is the highest obtained efficiency and VOC for the visible‐light active zwitterionic unsymmetrical‐squaraine dye with copper‐based electrolyte.