Cytochromes P450 are unique family of isozymes, discovered in all kingdoms of living species (in animals, bacteria, plants, fungi, archaea). The main functional role of the cytochromes P450 is biotransformation of exogenous and endogenous compounds. This review is highlighted problem of enchasing effectivity of electrocatalysis of cytochromes P450, enzymes that have unique capabilities both for biosensors’ design and for biotechnological application. In this review paper, we summarize main methods and modern trends based on biochemical mechanism of cytochromes P450 for development of reconstructing and electrochemical catalytic systems for practical application of these enzymes.