Smart clothing that integrates active luminescence and motion monitoring holds significant importance for enhancing safety during nighttime activities. In this study, by combining mechanoluminescent materials (ZnS/Cu) with triboelectric nanogenerators, an intelligent yoga pant that actively emits light and senses joint movements during physical activities has been fabricated. The incorporation of silver fiber electrodes ensures breathability throughout the mechanoluminescent triboelectric sensor (MTS), contributing to the high comfort of wearable smart clothing. The doping of ZnS/Cu with organic silicone rubber enhances the dielectric constant of the triboelectric layer, thereby effectively enhancing the output signal of the MTS. Moreover, the mechanoluminescent materials convert the tension applied during joint flexion into dynamically varying light, alerting passing vehicles and safeguarding users during nighttime activities. An in-depth investigation was conducted on the relationship between the content of luminescent materials and the device’s light intensity and output voltage under the same stretching conditions. The integration of a wearable signal acquisition system ensures real-time output of the electrical signals from the MTS during running, enabling online real-time monitoring of motion indicators such as joint bending angles and step counts. These findings provide feasible insights for the development of breathable, active luminescent smart clothing.