Firefighters need personal protection equipment and protective clothing to be safe and protected when responding to fire incidents. At present, firefighters’ suits are developed by using inherently thermal-resistant fibers but pose serious problems related to comfort. In the present research, multilayered fire-fighting fabrics were developed with different fiber blends. Multilayer fire retardant (FR) fabrics with phase change materials (PCMs) inserts were developed and compared with reference multilayer fabrics without PCM. In this context, four fabric samples were chosen to fabricate the multilayer FR fabrics. Properties of multilayer fabrics were investigated, which include physical, thermo–physiological comfort, and flame-resistant performance. The heating process of the clothing was examined using infrared (IR) thermography, differential scanning calorimetry (DSC), thermal protective testing (TPP), and steady-state (Convective and Radiant) heat resistance tests. Areal density and thickness were measured as physical parameters, and air permeability (AP), overall moisture management capacity (OMMC), and thermal conductivity were measured as thermo–physiological comfort characteristics. The inclusion of PCM improved the thermal protection as well as flame resistance significantly. Sample S1 (Nomex + PTFE + Nomex with PCM) demonstrated superior fire resistance, air permeability, and thermal protection, with a 37.3% increase in air permeability as compared to the control sample (SC) by maintaining comfort while offering high thermal resilience. The inclusion of PCM enhanced its thermal regulation, moderating heat transfer. Flame resistance tests confirmed its excellent performance, while thermo–physiological assessments highlighted a well-balanced combination of thermal conductivity and air permeability. This study will help to improve the performance of firefighter protective fabrics and provide guidelines in terms of balancing comfort and performance while designing firefighter protective clothing for different climatic conditions.