LaNiO3 is considered electromagnetic wave-absorbing material owing to its unique crystal structure and controllable dielectric constant. However, the effect of ion doping modification on microwave absorption performance remains to be thoroughly investigated. In this study, LaNi1−xBaxO3(x = 0, 0.02, 0.04, 0.06) was prepared through sol-gel methods. The reflection loss (RL) of the sample in the 2−18 GHz band was calculated using transmission line theory. Specifically, LaNi0.96Ba0.04O3 exhibited superior results, with an RL value of −34.54 dB at d = 3 mm and f = 6.80 GHz, indicating effective absorption within the C-band. These results suggest that adding an appropriate amount of Ba ions to the material can effectively regulate the electromagnetic parameters and optimize impedance matching. Introducing Ba ions into the crystal interior produces abundant defects, which provide active sites for multipolarization and ultimately improve the wave-absorbing properties of the material. In addition, radar cross section(RCS) simulations simulation after coating the samples on original ideal conductor (PEC) substrates provide support for potential practical applications of the material.