Primers are used to reliably initiate a secondary explosive in a wide range of industrial and defence applications. However, established primer technologies pose both direct and indirect risks to health and safety. This review analyses a new generation of primer materials and ignition control mechanisms that have been developed to address these risks in firearms. Electrically or optically initiated metal, oxide and semiconductor-based devices show promise as alternatives for heavy metal percussive primers. The prospects for wider use of low-cost, safe, reliable and non-toxic primers are discussed in view of these developments.