Global energy consumption has increased due to population growth and economic development. Solar energy is one of the most important renewable energy sources for human consumption. In this research, four novel organic dyes (D2–D5) of the D–A–π–A structure based on triphenylamine (TPA) were studied theoretically using DFT and TD-DFT techniques for future usage as dye-sensitized solar cells (DSSCs). The effects of modifying the π-spacer of the reference molecule D1 on the structural, electronic, photovoltaic, and optical characteristics of the D2–D5 dyes were studied in detail. D2–D5 exhibited band gaps (Egap) in the range from 1.89 to 2.10 eV with λabs in the range of 508 to 563 nm. The results obtained show that modifying the π-spacer of the dye D1 increased its hole injection and reinforced the intramolecular charge-transfer (ICT) impact, which resulted in a red-shifted ICT absorption with a greater molar extinction coefficient. The theoretically calculated open-circuit voltage (Voc) values ranged from 0.69 to 1.06 eV, while the light-harvesting efficiency (LHE) values varied from 0.95 to 0.99. Indeed, this theoretical research could guide chemists to synthesize effective dyes for DSSCs.