Fire and explosions in the processing of matchhead compositions are reported due to the friction sensitivity of materials used. This investigation is aimed at investigating the influence of different types of contact materials and their surface roughness on the friction sensitivity of a matchhead composition. The friction sensitivity of the matchhead composition was found to be dependent on the contact materials and their roughness. The results demonstrated that the contact materials and their surface roughness imparted variations to the sensitivity, ranging from 108 to 360N. The sensitivity response of the energetic mixture was quicker in case of aluminum plate-aluminum pin combinations than those when steel plate-steel pin and brass plate-brass pin combinations were used. For the first time, the experimental investigation identified a new value based on the material's surface roughnesses called critical surface roughness, at which the matchhead composition ignited at a minimum frictional load. The matchhead composition was found to be highly hazardous at the critical surface roughness values of 1.09, 1.01, and 1.05m for aluminum, brass, and steel surfaces, respectively. Based on the experimental results this paper also discusses mechanism of ignition caused by the frictional load.