The unique functional responses of electroactive biomolecules offer untapped opportunities for designing novel materials for molecular bioelectronics. Assembling these biomolecules into a geometric structure that provides rigidity, optical and/or electronic accessibility, and stability is critical for practical applications. The results presented here demonstrate that it is possible to establish electronic communication with a redox-active biomolecule immobilized within the porous structure of a sol-gel. The authors provide a viable approach to utilizing proteins and enzymes for bioelectronic device applications.