In this study, we have investigated the relationship between the plasma temperature in remote laser-induced breakdown spectroscopy (LIBS) experiments and the hydrophobic properties of silicone rubber insulators (SIRs). Contact angle and LIBS measurements were conducted on both artificially-aged (accelerated aging) and field-aged SIRs. This study reveals a clear connection between plasma temperature and the properties of aged SIRs on artificially-aged SIR specimens. Specifically, the plasma temperature exhibits a consistent increase with the duration of the accelerated aging test. The hydrophobicity of the artificially-aged SIRs was assessed by performing contact angle measurements, revealing a decrease in the hydrophobicity with increased aging test duration. Furthermore, we extended our investigation to the study of nine field-aged SIRs that had been in use on 150 kV overhead transmission lines for 0 to 21 years. We find that the laser absorption and hardness of the material do not relate to the plasma temperature. In summary, we observe a direct connection of plasma temperature to both contact-angle measurements and operation time of the in-service insulators. These results strongly suggest the potential use of LIBS for remotely evaluating the hydrophobicity and aging degree of silicone rubber insulators, thus assessing their real-time on-site operational quality.