Complex Fenestration Systems (CFS) are advanced daylighting systems that are placed on the upper part of a window to improve the indoor daylight distribution within rooms. Due to their double function of daylight redirection and solar protection, they are considered as a solution to mitigate the unfavorable effects due to the admission of direct sunlight in buildings located in prevailing sunny climates (risk of glare and overheating). Accordingly, an adequate assessment of their performance should include an annual evaluation of the main aspects relevant to the use of daylight in such regions: the indoor illuminance distribution, thermal comfort, and visual comfort of the occupant’s. Such evaluation is possible with the use of computer simulations combined with the bi-directional scattering distribution function (BSDF) data of these systems. This study explores the use of available methods to assess the visible and thermal annual performance of five different CFS using advanced computer simulations. To achieve results, an on-site daylight monitoring was carried out in a building located in a predominantly sunny climate location, and the collected data was used to create and calibrate a virtual model used to carry-out the simulations. The results can be employed to select the CFS, which improves visual and thermal interior environment for the occupants.