Many chemical reactions of industrial importance involve complex reaction pathways and networks; and the determinations of the reaction rate laws are very difficult. The accurate or proper rate expression is the most desired information in design phase however. In this study, the network reduction technique and the Bodenstein approximation of quasi-stationary behavior of reaction intermediates were systematically applied to derive general rate and instantaneous rate ratio equations for multi-pathway reaction networks in homogeneous catalysis or enzyme system. Multiple small reaction cycles in a main cycle, and multiple-pathways stemming from an intermediate and ending at different nodes in a cycle were considered. The general rate and rate ratio equations derived in this study are applicable for most homogeneous catalytic reactions and enzymatic reactions. Two examples of multi-pathway cyclic enzyme reaction were used to illustrate the applications of the general rate and rate ratio equations for network elucidation.