The photoproduced cation radical of N-methylphenothiazine doped in the different kind of matrices of phenyltriethoxysilane (PhiTEOS), vinyltriethoxysilane (VTEOS), and methyloiethoxysilane (METOS) was comparatively studied with electron spin resonance (ESR) and electron nuclear double resonance (ENDOR). The photoinduced charge separation efficiency was determined by integration of ESR spectra which correspond to the amount of photoproduced cation radical in the matrices. This was correlatively studied with the polarity and pore size of the gel matrices. The polarity of the matrices was comparatively determined by measuring λ$sub$max/ values of PC$_1$ in the different matrices. The relative pore size among the matrices was determined by measuring relative proton matrix ENDOR line widths of the photoproduced cation radical of PCI. The decay kinetic constants of the cation radical of PCI in the different matrices was relatively studied with fitting the biexponential decay curves after exposure into the ambient condition. This is correlatively interpreted with the polarity and pore size of the matrices.