Under the global trend of green development, the research and development of environmentally friendly gas-insulated electrical equipment and the associated technical issues in the power systems industry have become important research topics. This study investigates the monitoring technology for decomposition gases (CO, C2F6, and COF2) under insulation defect conditions in environmentally friendly GIS equipment based on the green insulating gas mixture C4F7N/CO2. Initially, chromium clusters (Crn, n = 1–4) were used to modify one-dimensional boron nitride nanotubes (BNNTs), describing the changes in semiconductor electronic properties and magnetism at the microscopic interface. Interestingly, the electronic properties of the system changed significantly after modification, with increased electron mobility and enhanced conductivity. Subsequently, adsorption tests were conducted on three potential target gases, revealing that Cr-BNNT exhibited excellent adsorption for COF2, with an adsorption energy reaching -9.555 eV. This indicates its potential as a clean material for addressing COF2 (toxic) and CO leaks. Lastly, and most importantly, in the assessment of sensing performance, it has been discovered that Cr-BNNT holds promise as a gas sensor for C2F6. Furthermore, to meet diverse sensing requirements and environmental conditions, Cr3-BNNT and Cr4-BNNT have demonstrated potential as sensor array materials for the detection of CO (300 K, 0.145 μs) and COF2 (500 K, 3 min) gas concentrations, respectively. Our study contributes to the advancement of novel eco-friendly insulating gases and explores the use of new materials for monitoring the insulation performance and condition assessment of environmentally friendly GIS equipment.