A review on the catalytic oxidative cracking of light alkanes to alkenes is presented as an alternative route to steam cracking for production of alkenes. Catalytic oxidative cracking is a combination of heterogeneous and homogeneous reactions; the reaction is initiated on the catalyst surface followed by thermal gas phase cracking. The review focuses on the catalytic generation of alkyl radicals at moderate temperatures (550–650 °C) using the Li/MgO system. Comparison with other catalyst systems such as Li/Y2O3, Au/La2O3, Au-SCZ, BiOCl, B2O3/Al2O3, Co-N/Al2O3 and Pt/Al2O3 monoliths is included. Gold supported on sulfated ceria-zirconia catalyst (Au-SCZ) is concluded to be a promising catalyst for further study. In addition to catalytic initiation of radicals, the review discusses alkyl generation using non-equilibrium plasma. Plasma-catalysis in oxidative cracking induces synergy effects and introduces significant improvement in yields of alkenes; however, further understanding of plasma chemistry needs to be elaborated. Minimizing CO2 production and maximizing yields of valuable C2–C4 alkenes remains the bottleneck for the commercialization of oxidative cracking process. Future research should focus on reactor design and on developing optimized reactor-catalyst systems.