An electronic nose (e-nose) utilizes a multisensor array, which relies on the vector contrast of combinatorial responses, to effectively discriminate between volatile organic compounds (VOCs). In recent years, hierarchical structures made of nonbiological materials have been used to achieve the required sensor diversity. With the advent of self-assembling peptides, the ability to tune nanostructuration, surprisingly, has not been exploited for sensor array diversification. In this work, a designer surfactant-like peptide sequence, CG$_7$–NH$_2$, is used to fabricate morphologically and physicochemically heterogeneous “biohybrid” surfaces on Au-covered chips. These multistructural sensing surfaces, containing immobilized hierarchical nanostructures surrounded by self-assembled monolayers, are used for the detection and discrimination of VOCs. Through a simple and judicious design process, involving changes in pH and water content of peptide solutions, a five-element biohybrid sensor array coupled with a gas-phase surface plasmon resonance imaging system is shown to achieve sufficient discriminatory capabilities for four VOCs. Moreover, the limit of detection of the multiarray system is bench-marked at <1 and 6 ppbv for hexanoic acid and phenol (esophago-gastric biomarkers), respectively. Finally, the humidity effects are characterized, identifying the dissociation rate constant as a robust descriptor for classification, further exemplifying their efficacy as biomaterials in the field of artificial olfaction.