Pseudo invariant calibration sites (PICS) have been used for on-orbit radiometric trending of optical satellite systems for more than 15 years. This approach to vicarious calibration has demonstrated a high degree of reliability and repeatability at the level of 1-3% depending on the site, spectral channel, and imaging geometries. A variety of sensors have used this approach for trending because it is broadly applicable and easy to implement. Models to describe the surface reflectance properties, as well as the intervening atmosphere have also been developed to improve the precision of the method. However, one limiting factor of using PICS is that an absolute calibration capability has not yet been fully developed. Because of this, PICS are primarily limited to providing only long term trending information for individual sensors or cross-calibration opportunities between two sensors. This paper builds an argument that PICS can be used more extensively for absolute calibration. To illustrate this, a simple empirical model is developed for the well-known Libya 4 PICS based on observations by Terra MODIS and EO-1 Hyperion. The model is validated by comparing model predicted top-of-atmosphere reflectance values to actual measurements made by the Landsat ETM+ sensor reflective bands. Following this, an outline is presented to develop a more comprehensive and accurate PICS absolute calibration model that can be Système international d'unités (SI) traceable. These initial concepts suggest that absolute calibration using PICS is possible on a broad scale and can lead to improved on-orbit calibration capabilities for optical satellite sensors.