In this work, the effects of interactions among polyaniline (PAn), camphorsulfonic acid (CSA), and silica on the structure and properties of their sol-gel hybrids are investigated. These interactions were revealed by FTIR, UV-vis spectra, and XRD patterns. The interaction between PAn and CSA raises conductivities of the CSA-doped PAn/SiO2 (c-PAn/SiO2) hybrids. Moreover, the hydrogen bonding interaction between c-PAn and silicic acid (precursor of SiO2) leads to a less degree of three-dimensional network structure of the SiO2 component in a hybrid with higher PAn content. In addition, because of the interactions among CSA, Pan, and SiO2, the conductive c-PAn-rich phase distributes uniformly in the hybrid and thermal resistance of the hybrid is enhanced consequently. Besides, the c-PAn/ SiO2 hybrid with higher SiO2 content exhibits more significant blue-shift of its polaron band, lower conductivity, and higher thermal resistance.