We report the synthesis and the optoelectronic characterization of three new 4H-pyran-4-ylidene and thiazole derivatives (pyt) as metal-free organic dyes for solid-state dye-sensitized solar cells (DSSCs). We investigate the performance and the long-term stability of devices employing pyt dyes functionalized with carboxylic and phosphonic acids as TiO2 anchoring groups. In contrast to reports on liquid electrolyte DSSCs, we show that solid-state DSSCs prepared with phosphoric pyt derivatives can achieve similar power conversion efficiency to their carboxyl analogues. We make use of the Mott-Schottky analysis and equivalent circuit models to demonstrate that a phosphonic group induces a significant increase in built-in voltage at the TiO2-hole transporter interface, which results in a higher open circuit voltage.