Multienzymatic cascade reactions are a most important technology to succeed in industrial process development, such as synthesis of pharmaceutical, cosmetic, and nutritional compounds. Different strategies to construct multienzyme structures have been widely reported. Enzymes complexes are designed by three types of routes: (i) fusion proteins, (ii) enzyme scaffolds, or (iii) immobilization. As a result, enzyme complexes can enhance cascade enzymatic activity through substrate channeling. In particular, recent advances in materials science have led to syntheses of various materials applicable for enzyme immobilization. This review discusses different cases for assembling multienzyme complexes via random co-immobilization, compartmentalization, and positional co-immobilization. The advantages of using immobilized multienzymes include not only improved cascade enzymatic activity via substrate channeling but also enhanced enzyme stability and ease of recovery for reuse. In this review, we also consider the latest studies of different model enzyme reactions immobilized on various support materials, as multienzyme systems allow for economical product synthesis through bioprocesses.