Two novel metal-free dyes (DPP-I and DPP-II) with a diketopyrrolopyrrole (DPP) core were synthesized for dye-sensitized solar cells (DSSCs). The absorption spectra and electrochemical and photovoltaic properties of DPP-I and DPP-II were extensively investigated. Electrochemical measurement data indicate that the tuning of the HOMO and LUMO energy levels can be conveniently accomplished by alternating the π-conjugated systems. Besides, coadsorption of chenodeoxycholic acid (CDCA) can hinder the formation of dye aggregates and might improve electron injection yield and, thus, Jsc. This has also led to a rise in the photovoltage, which is attributed to the decrease of charge recombination. The DSSC based on dye DPP-I showed better photovoltaic performance: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 80%, a short-circuit photocurrent density (Jsc) of 9.78 mA cm−2, an open-circuit photovoltage (Voc) of 605 mV, and a fill factor (FF) of 0.69, corresponding to an overall co...