Abstract Predicting and optimizing radiative thermal properties have been acknowledged as an efficient way to improve thermal insulation performance of fibrous materials with high porosity. Based on experimental investigation of infrared spectral of ultrafine fibrous insulations with diameters of 520–650 nm, a method of calculating radiative thermal properties was presented by combining Rosseland equation, Mie scattering theory, Beer’s law and Subtractive Kramers–Kronig (SKK) relation. To ensure the calculation correct the uniqueness analysis was performed for Poly(vinylidene fluoride) (PVDF) fibers, which indicated the valid fiber diameter was less than 1.06 μm. The calculated thermal radiative conductivities by using the method agreed well with the measured data. The effect of fiber diameter on the thermal properties of the fibrous insulations was also investigated to minimize the radiative thermal conductivity. The results indicated that the minimized radiative thermal conductivities by regulating fiber diameters could be approximately 25% smaller than those for experimental fiber diameters. The method of predicting and minimizing radiative thermal conductivities of fibrous insulations demonstrated in this paper could be of great advantage to thermal engineering applications aiming to reducing heat loss and saving energy.