Alloying secondary hardening steels with Ni and Al allows the precipitation of an intermetallic phase B2-NiAl in addition to the classical secondary carbides precipitation, adding up the advantages of both types of precipitation (Erlach et al. Mater Sci Eng A 429:96, 2006; Erlach et al. Int J Microstruct Mater Prop 3:373, 2008). Small-angle neutron scattering experiments were carried out to analyse the nanometric scale precipitation of a martensitic steel containing a double precipitation of carbides and intermetallic phase. The precipitates size, volume fraction and chemical composition for both carbides and intermetallic phases according to the tempering time were estimated and discussed. In addition, experimental cobalt-free grades containing a single precipitation or a double precipitation were manufactured and analysed. Relationship between measured tensile yield strengths and the nanometre-sized particles are suggested, showing that both populations of precipitates have a relevant impact on the mechanical properties.