In search for the probability of p-n junction in the quasi-solid (QS) phase in the multi-semiconductor specimen (MSS) altogether with the development of the DSSC electrolyte optimization technique, there are three major things to be considered: 1) the hypothesis for a theoretical redox-conductivity (Ip−σ) correlation on the better understanding of advanced cyclic voltammetry (CV) analysis using a mathematical axiom correlation method, 2) the concept of p-n junction possibility based on the solid-phase (SP) hypothetical projection, and 3) the observational and optimization for x-TiO2/Cs/KI-I2. To prove the p-n junction existence in a QS-MSS, we develop a series of methods by using advanced analysis of voltammogram, which are 1) defining the chitosan as a conductive polymer to a certain extent, 2) understanding the influence of different wt% x-TiO2 on the redox activity of QS-MSS, and 3) the different crystal system of TN(10)†,‡ that are anatase-rutile (a-r) and rutile-anatase (r-a) dominant phase are influencing the Ip. Moreover, the analyses consist of a series of modified-dimensionless parameter, ψ, to define the modified-diffusional coefficient, Dx2, definition and electronical transferal rate, k0, as well. Furthermore, the crucial observation is by looking at the valence and conduction band (vb-cb) for each sample, respectively, to determine the position toward the hypothetical projection in the DSSC system later. Moreover, we found that a hypothetical development on the Ip−σ modified function is needed. Also, the use of the vb-cb value is crucial to project a unified rule of p-n junction theory approximation from electrolyte to dye.