From the point of view of green analytical chemistry (GAC), methods based on direct analysis must be considered the ideal approach because they do not involve sample handling or the use of reagents and/or solvents and they do not generate waste, thus reducing contamination and analyte loss risks together with a minimum impact on the environment. In this chapter, direct measurements based on the use of spectroscopic and spectrometric techniques are presented, taking into consideration their versatility and capability to be used for the analysis of samples in different physical states. These techniques are discussed considering the potential damage to the sample, after measurements, their non-invasive characteristics and their non-destructive capability. Measurement strategies for mineral and molecular analysis are discussed and the possibilities of the use of remote sensing and teledetection systems are considered as analytical tools that agree with the principles of GAC. The role of chemometrics and the emerging image processing-based methods and their contribution to the democratization of analytical chemistry are also discussed.