Spontaneous ignition begins inside the substance as a process of exothermic reactions, which are accompanied by flame and flameless combustion, with no initiation from the external environment. We recognize several types of autoignition, namely physico-chemical, chemical and biological. The bachelor thesis describes these processes and factors conditioning the occurrence of spontaneous ignition, the circumstances of the transport of hazardous substances capable of spontaneous ignition, their classification and labeling. The actual part of the work is focused on the description of some types of self-igniting substances (white phosphorus, dill and coal), their physico-chemical properties, transport conditions and safe handling. Based on a theoretical analysis, it can be said that white phosphorus is pyrophoric, so at the contact with air it immediately burns and releases dense white toxic smoke. The process of spontaneous ignition of dill occurs when there is insufficient ventilation and also under the influence of enzymes. In addition to dill, it is necessary to comply with the ventilation criteria for coal. Factors that affect the process of spontaneous ignition of coal are the initial temperature and the amount of humidity in it.