Copper appears to be an indispensable ingredient of non-asbestos organic (NAO) brake friction materials owing to its multifunctionality. However, recent findings proved it as a threat to aquatic life and efforts were initiated worldwide over the last few years to find a substitute for it. Recently, the authors’ group had reported on the potential of particulate Promaxon-D (hydrated calcium silicate), a porous material for enhancement of noise–vibration (NV) performance of Cu-free brake pads. It was felt necessary to investigate how Promaxon-D (PD) contributes to controlling tribo-performance of brake pads since this aspect is most important for the brake friction materials. A series of five types of brake pads was developed by keeping parent composition fixed and varying the theme ingredient PD content from 0–20 wt.%. The tribo-performance was evaluated on a full-scale brake inertia dynamometer as per the JASO C406 test standards. The increase in PD contents led to a reduction in density, hardness, and thermal conductivity while an increase in porosity and compressibility. With the increase in PD contents, almost all tribo properties such as average μ, fade ratio, and recovery ratio got enhanced, sensitivity of µ for pressure, speed, and temperature lowered but at the cost of wear resistance. Finally, the worn surfaces of pads and discs were observed under a scanning electron microscope equipped with energy dispersive X-ray (SEM-EDX) to find out the presence of various elements at the contact zone and to monitor specific topographical events responsible for wear mechanism.