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The TiO2 thin film, Ag NP and three Ag‐NP/TiO2 composite thin films (COMP‐Agn;n = 20, 50, and 75 Ag mol%) were successfully fabricated on quartz glass. The optical properties of the composite electrodes were investigated, and the results indicate a surface plasmonic resonance peak at 410 nm while the electrical resistivity of the composite thin films improved up to 6.9 × 10−5 Ω cm. The photo‐response threshold of the Ag‐NP/TiO2 composite thin films was enhanced and shifted into the visible and near‐infrared when the chlorophyll dye was adsorbed onto them. The hall effect was performed on the fabricated thin films and the charge carrier concentrate value confirmed that the Ag/TiO2 with Ag concentrate >45% are found to be p‐type. The n‐types were observed till the Ag content in TiO2 was increased up to 45 mol%. COMP‐Ag75 has a charge carrier concentration of 1.3 × 10−19 cm−3 as a p‐type electrode was then employed to construct a p‐DSSC. Such enhancement on photovoltaic activity can be attributed to the generated Z‐scheme system in the anatase/rutile phase‐junction Ag/TiO2 photocathode enhances the separation, diffusion, and transformation of electron/hole pairs inside the structure. This p‐DSSC exhibits a photon‐electrical conversion efficiency (PCE) of 0.37%. The PCE recorded is equal to or greater than those of traditional high‐efficiency n‐DSSCs. This allows the creation of a new generation of photocathodic p‐DSSCs with previously unheard‐of unprecedentedly high concentrations of Ag (up to 80 mol%) evenly scattered in a TiO2 matrix, and this efficacy is the highest ever reported for a p‐type working Ag/TiO2/chlorophyll/iodine electrode. This may enable the use of this electrode as a component of photosensitizer tandem devices. Highlights: ▪The 75 mol% Ag/TiO2 composited higher conductive p‐type electrode was fabricated.▪The Electrode found to have a visible plasmon peak at 410 nm and electrical conductivity of 6.7 × 10−5 cm.▪This p‐type electrode was then employed as a working electrode to construct a p‐DSSC.▪This p‐DSSC exhibits a photon‐electrical conversion efficiency (PCE) of 0.37%.▪Although the PCE is lower, this electrode can be a component of photosensitizer tandem devices. [ABSTRACT FROM AUTHOR]