The application of perovskite photovoltaics is hampered by issues related to the operational stability upon exposure to external stimuli, such as voltage bias and light. The dynamic control of the properties of perovskite materials in response to light could ensure the durability of perovskite solar cells, which is especially critical at the interface with charge-extraction layers. We have applied a functionalized photochromic material based on spiro-indoline naphthoxazine at the interface with hole-transport layers in the corresponding perovskite solar cells with the aim of stabilizing them in response to voltage bias and light. We demonstrate photoinduced transformation by a combination of techniques, including transient absorption spectroscopy and Kelvin probe force microscopy. As a result, the application of the photochromic derivative offers improvements in photovoltaic performance and operational stability, highlighting the potential of dynamic photochromic strategies in perovskite photovoltaics.