In this study, analytical solution of multip-species transport equations coupled with a first-order reaction network under constant concentration boundary condition or total flux boundary condition is obtained using similarity transformation approach of Clement et al. (2000). The study shows the schematic process about how multi-species transport equations with first-order sequential reaction network is transformed through the similarity transformation approach into independent and uncoupled single species transport equations with first-order reaction. The analytical solution was verified through the comparison with popular commercial programs such as 2DFATMIC and RT3D. The analytical solution can be utilized in nuclear waste sites where radioactive contaminants and their daughter products occur and in industrial complex cities where chlorinated solvent such as PCE, TCE, and its biodegradation products produces. In addition, it can help the verification of the developed numerical code.