The anti-reflection (AR) technology currently used in photovoltaic (PV) glass has reached its operational limit as the refractive index of existing materials cannot be lowered further. To overcome this, in this study, we selected formed methylsiloxane as an AR layer for PV glass. Its low refractive index (∼1.37) originates from the high content of methyl groups and the formation of voids during crosslinking. We acquired and compared the refractive index curves, conducted structural analyses, characterizations (optical, thermal, and surface), and performance evaluations to confirm the advantages of silicone as an AR layer for PV panels. The spreading and subsequent room-temperature self-curing characteristics of silicone considerably enhanced its applicability for upscaling and repair. The hydrophobic nature of the silicone AR layer imparted a new self-cleaning function to the solar panels; further, the methyl-silicone coating enhanced light transmission, resulting in electrical gain. Furthermore, the addition of the methyl-silicone layer created a refractive index gradient on the glass surface, making it fully compatible for use with the mainstream AR process, namely, the sol-gel method employed for PV glass.