Iron‐alkyl complexes are found as intermediates in a variety of homogenous organometallic reactions. The chapter deals with the synthesis, stability and reactions of iron‐alkyl complexes. Wilkinson and Piper in 1956 were the first to report an iron‐alkyl complex, and these investigations lead to the discovery of a whole range of reactions involving these complexes. This chapter will firstly cover the preparation of iron‐alkyl complexes, followed by the main categories of reactions in which these complexes take part, mainly CO insertion reactions and electrophilic cleavage reactions. A brief account of the role of FpMe (Fp = CpFe(CO)
2
) complexes in catalytic processes are also included in this chapter.