They both look very late Victorian to early Edwardian, as in 1897 - 1907. Hard for me to be sure without seeing some close ups, especially close ups of the interiors. The black hat seems a bit odd to me because the brim, its construction, and the lining are circa 1900 era but the crown and especially the green ribbon looks newer than that to me. Is it possible that the ribbon was added at some later date? As I said I would need to see it close and examine the joins and the sewing, etc. Is the ribbon a heavy silk satin?
The second (beige?) hat is an interesting novelty straw, very nice. It probably had a lining which is now gone missing, although not all straw hats had linings especially is they had a sheer silk facing as yours does. The ties may be additions.