The development of analytical techniques for antioxidant compounds is important, because antioxidants that can inactivate reactive species and radicals are health-beneficial compounds, also used in the preservation of food and protection of almost every kind of organic substance from oxidation. Energetic substances include explosives, pyrotechnics, propellants and fuels, and their determination at bulk/trace levels is important for the safety and well-being of modern societies exposed to various security threats. Most of the time, in field/on site detection of these important analytes necessitates the use of colorimetric sensors and probes enabling naked-eye detection, or low-cost and easy-to-use fluorometric sensors. The use of nanosensors brings important advantages to this field of analytical chemistry due to their various physico-chemical advantages of increased surface area, surface plasmon resonance absorption of noble metal nanoparticles, and superior enzyme-mimic catalytic properties. Thus, this critical review focuses on the design strategies for colorimetric sensors and nanoprobes in characterizing antioxidant and energetic substances. In this regard, the main themes and properties in optical sensor design are defined and classified. Nanomaterial-based optical sensors/probes are discussed with respect to their mechanisms of operation, namely formation and growth of noble metal nanoparticles, their aggregation and disaggregation, displacement of active constituents by complexation or electrostatic interaction, miscellaneous mechanisms, and the choice of metallic oxide nanoparticles taking part in such formulations.