AbstractDeveloping a green and energy‐saving alternative to the traditional Haber‐Bosch process for converting nitrogen into ammonia is urgently needed. Imitating from biological nitrogen fixation and photosynthesis processes, this work develops a monolithic artificial leaf based on triple junction (3J) InGaP/GaAs/Ge cell for solar‐driven ammonia conversion under ambient conditions. A gold layer serves as the catalytic site for nitrogen fixation with photogenerated electrons. The Au/Ti/3J InGaP/GaAs/Ge photoelectrochemical (PEC) device achieves high ammonia production rates and Faradaic efficiencies in a two‐electrode system without applying external potential. For example, at 0.2 sunlight intensity, the solar‐to‐ammonia (STA) conversion efficiency reaches 1.11% and the corresponding Faradaic efficiency is up to 28.9%. By integrating a Ni foil on the anode side for the oxygen evolution reaction (OER), the monolithic artificial leaf exhibits an ammonia production rate of 8.5 µg cm−2h at 1.5 sunlight intensity. Additionally, a 3 × 3 cm unassisted wireless PEC device is fabricated that produces 1.0039 mg of ammonia in the 36‐h durability test. Thus, the new artificial leaf can successfully and directly convert solar energy into chemical energy and generate useful products in an environmentally friendly approach.