The role of iron(III) oxide (Fe2O3) in the cross-linking process, structure and functional properties of chloroprene and butadiene rubber (CR/BR) blends was studied. The unconventional elastomeric blends containing chloroprene and butadiene rubbers of different mass ratios, cross-linked with iron(III) oxide, have been studied. It has found that the iron(III) oxide could be used as a cross-linking agent in CR/BR blend and the curing degree depends largely on the composition of the blends. These results indicate that the curing degree of the blends is increased with increasing amount of chloroprene rubber. It is very interesting to note that the addition of butadiene rubber to chloroprene rubber improved the mechanical properties of the resulting vulcanizates. The resulting CR/BR/Fe2O3 vulcanizates were characterized by good mechanical properties. Surprisingly, the selected vulcanizates containing chloroprene and butadiene rubbers had a 40% greater tensile strength compared to vulcanizates containing only chloroprene rubber. The amount of iron(III) oxide as the curing agent slightly affected the curing degree and mechanical properties of the resulting rubber materials. This should probably be linked to the interelastomer reaction between the chloroprene and butadiene rubbers occurring in the presence of iron(III) oxide at an elevated temperature. Interelastomer reactions between both elastomers may lead to improved homogeneity and miscibility of the test systems. Additionally, it has been found that the CR/BR blends cross-linked with Fe2O3 were characterized by a high flame resistance. The undoubtable advantages of the proposed technology are its simplicity, low cost and incombustibility.