The advancement of the photovoltaic technology is closely linked to the standard evaluation of the product, the diagnosis of problems, the validation of materials and cell properties, and the engineering and documentation of the ensemble of device properties from internal interfaces through power outputs. The focus of this paper is on some of the more common, visible, and important techniques dealing with physical-chemical through electro-optical parameters, which are linked intimately to the performance quality of materials and devices. Two areas, defined by their spatial-resolution qualities, are emphasized: macroscale and microscale measurement technologies. The importance, strengths, and limitations of these techniques are stressed, especially their significance to photovoltaics. Included are several techniques that have been developed specifically to address problems and requirements for photovoltaics. The regime of measurement literally covers arrays through atoms.