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The ability of a structure in the form of a photovoltaic element with a built-in posistor layer based on a polymer nanocomposite with carbon filler being in direct thermal contact to protect against overvoltages was studied experimentally and by simulation. It was shown that the current and voltage on the reverse-biased p–n junction of the photovoltaic layer are limited and decrease from the moment when the temperature of this structure reaches values close to the tripping temperature of the posistor nanocomposite to the low-conductivity state. The temperature of the photovoltaic layer has a value close to the tripping temperature of the posistor layer, which is equal to ∼125∘C. The possibility of realizing protection against reverse electrical overvoltages and thermal breakdown of photovoltaic systems based on photovoltaic elements with built-in layers of posistor polymer nanocomposites with carbon fillers was established.