Accurate estimation of the solar vacuum ultraviolet irradiance between 0.1 and 200 nm is critical for the study of planetary aeronomy. Previous empirical models have relied on a limited number of reference spectra, or on multiple data sets with various degrees of uncertainty, and on an empirical selection of solar proxies. Here we propose a novel method for the development of empirical models based on Fourier transform and least-squares fitting of the long-term measurements from the Solar EUV Experiment on the Thermosphere Ionosphere Mesosphere Energetics and Dynamics mission. A Fourier transform analysis is performed to examine a large number of solar proxies, which reveals that the solar radio flux at 10.7 cm and the solar Lyα flux at 121.6 nm are better proxies for solar irradiance below and above ∼120 nm, respectively. Using these two proxies, a nonlinear empirical model is developed through Fourier transform and least-squares fitting of solar irradiance measurements, which can reproduce the solar irradiance with uncertainties of only ∼1%–2% above ∼120 nm, ∼2%–4% within ∼45–120 nm, and ∼4%–8% below ∼45 nm. Comparison with measurements from the Extreme Ultraviolet Monitor on the Mars Atmosphere and Volatile Evolution mission indicates that the solar irradiance at Mars can be predicted with uncertainties of less than ∼8% by geometric extrapolation of the solar irradiance measured from Earth, provided that the measurements from Earth can be calibrated accurately. Our study provides a general method for the development of empirical models using long-term observations in planetary aeronomy.