Optical-based remote sensing offers great potential for phenotyping vegetation traits and functions for a range of applications including vegetation monitoring and assessment. A key strength of optical-based approaches is the underlying mechanistic link to vegetation physiology, biochemistry, and structure that influences a spectral signal. By exploiting spectral variation driven by plant physiological response to environment, remotely sensed products can be used to estimate vegetation traits and functions. However, oftentimes these products are proxies based on covariance, which can lead to misinterpretation and decoupling under certain scenarios. This viewpoint will discuss (i) the optical properties of vegetation, (ii) applications of vegetation indices, solar-induced fluorescence, and machine-learning approaches, and (iii) how covariance can lead to good empirical proximation of plant traits and functions. Understanding and acknowledging the underlying mechanistic basis of plant optics must be considered as remotely sensed data availability and applications continue to grow. Doing so will enable appropriate application and consideration of limitations for the use of optical-based remote sensing for phenotyping applications.