Daylight availability knowledge is the first step for an energetic and visually efficient building and city design. It can be estimated with the Vertical Sky Component (VSC), which is defined as the ratio of the vertical diffuse illuminance over the unobstructed horizontal diffuse illuminance, simultaneously measured at the same point. These illuminance magnitudes are obtained from luxmeter measurements but these data are scarce. Alternatively, VSC can be obtained from prior knowledge of the sky illuminance distribution, which can be measured with a sky scanner device or by reference to the CIE (Commission Internationale de L’Éclairage) Standard classification for homogeneous skies. Both approaches are compared in this study. The coherence of the results obtained for the four cardinal orientations are analyzed by applying classical statistical parameters and luxmeter measurements as references for the results. The measurement campaign was completed between September 2016 and January 2019 in Burgos (Spain), as representative case study and specific contribution of this work. It was observed that the VSC values were higher than 100 in many cases: 21.94% for the south- and 33.6% for the east-facing vertical surfaces. The study highlights the good daylighting conditions in Burgos, mainly due to the predominance of clear skies over much of the year. This fact implies high daylight availability that, with efficient city planning and building design, could potentially lead reduction energy consumption of buildings, improvements in visual comfort, and the well-being of occupants.