We present initial results from the Wide-field Infrared Survey Explorer (WISE), a four-band all-sky thermal infrared survey that produces data well suited for measuring the physical properties of asteroids, and the NEOWISE enhancement to the WISE mission allowing for detailed study of solar system objects. Using a NEATM thermal model fitting routine, we compute diameters for over 100000 Main Belt asteroids (MBAs) from their IR thermal flux, with errors better than 10%. We then incorporate literature values of visible measurements (in the form of the H absolute magnitude) to determine albedos. Using these data we investigate the albedo and diameter distributions of the Main Belt. As observed previously, we find a change in the average albedo when comparing the inner, middle, and outer portions of the Main Belt. We also confirm that the albedo distribution of each region is strongly bimodal. We observe groupings of objects with similar albedos in regions of the Main Belt associated with dynamical breakup families. Asteroid families typically show a characteristic albedo for all members, but there are notable exceptions to this.