Upper left: Urraca de Palma (ウラカ・デ・パルマ)
Lower left: Rachel (レイチェル)
Middle-upper left: Seilurn (セイルーン)
Middle-lower left: Balud Antrim Cornelius (バルド・アントリム・コルネリアス)
Middle-upper right: Serina (セリーナ)
Middle-lower right: Silk Randolph (シルク・ランドルフ)
Upper right: Satsuki Kagetsu (サツキ・カゲツ)
Lower right: Agatha (アガサ)
I don't know when Urraca will join the harem, but I believe it's way after Balud conquers Haurelia. The image originates from volume 12 of the light novel (latest is volume 14). While there are not many spoilers out there, the Japanese Wikipedia has some. Also, the cover of the novels are pretty telling, if you're interested. See this one for example:
The story of the manga is currently around volume 4 of the light novel. I know for sure that Urraca is besides Balud by volume 8, same with Satsuki, which is way after the arc in Serina's country and after the Cornelius twins, Nigel and Marguerite, are born.