In this work, a novel algorithmic approach to detect multiplicity of steady states in enzymatic reaction networks is presented. The method exploits the structural properties of networks derived from the Chemical Reaction Network Theory. In first instance, the space of parameters is divided in different regions according to the qualitative behavior induced by the parameters in the long term dynamics of the network. Once the regions are identified, a condition for the appearance of multiplicities is checked in the different regions by solving a given optimization problem. In this way. the Method allows the characterization of the whole parameter space of biochemical networks in terms of the appearance or not of multistability. The approach is illustrated through a well-known case of en:dynamic catalysis with substrate inhibition. (C) 2009 American Institute of Chemical Engineers Biotechnol. Prog., 25: 619-631, 2009