This review is focused on the current state-of-the art of low-temperature electrochemistry and spectroelectrochemistry applied for coordination and organometallic compounds. From the first tentative steps in the 1960s to the present sophisticated spectroelectrochemical systems, low-temperature studies of redox reactions and coupled chemical processes have always fascinated chemists. The main reason is that low temperature offers the possibility not only to quantify thermodynamics/kinetics of electron transfer reactions, but also to better decipher mechanistic pathways of chemical-coupled electron transfer reactions. Various cryo-electrochemical and spectroelectrochemical set-ups have been designed leading to significant advancement of in situ detection of transient and unstable species generated by electrochemistry. In this review, we detail the novel aspects which can be discovered by performing electrochemical/spectroelectrochemical investigations at low temperature, and the means to carry out resolved electrochemistry at temperatures close to the liquid nitrogen solidification. Specific examples are given to demonstrate the powerful information which can be taken from low-temperature studies for coordination and organometallic chemistry. A conclusion and outlooks are also presented to discuss about the perspectives and remaining challenges for this research field.