The characters in the series include but are not limited to:
Llama (ラマ Rama?)
- Voiced by: Daisuke Ono
A llama who likes grass and dreams of becoming a popular animal at the zoo just like Panda.
Polar Bear (シロクマ Shirokuma?)
- Voiced by: Takahiro Sakurai
A polar bear who runs Polar Bear's Café, which is popular with both humans and animals. He has a habit of making bad puns with his customers and friends, just for the amusement of hearing their retorts.
Grizzly (グリズリー Gurizurī?)
- Voiced by: Yūichi Nakamura
A grizzly bear who is a childhood friend of Polar Bear. He runs a bar in the middle of town and has a rather fierce personality, though occasionally shows a soft side. He also usually serves as the tsukkomi to the antics of Polar Bear and Panda just like Penguin, a feature that curiously approached them to the point of becoming good friends.
Full Time Panda (常勤パンダ Jōkin Panda?)
- Voiced by: Katsuyuki Konishi
An older Giant Panda who works full time at the zoo along Panda. He is married and father of three, working hard to make ends meet for his family.
- Voiced by: Jun Fukuyama
A lazy, kind-hearted Giant Panda who works part-time at a petting zoo. He enjoys lazing around and eating bamboo and only orders iced coffee at the café until Polar Bear adds bamboo to the menu only for his sake. He is obsessed with all panda products and has a tendency to point out his popularity at the zoo and his own cuteness.
Mei Mei (メイメイ?)
- Voiced by: Kana Hanazawa
Panda's little sister with a crush on Handa whom she deems as handsome as a prince due to his short and chubby panda-like figure.
- Voiced by: Toshiyuki Morikawa
Panda and Mei Mei's mother who usually reprimands her son when he gets too lazy.
- Voiced by: Katsuyuki Konishi, Tomokazu Sugita, and Daisuke Hirakawa respectively
Three penguins each representing a member of the genus Pygoscelis who come with a plan to have people learn the differences between the different species of penguins by developing a deck of penguin-related cards. However the cards end up being a commercial failure.
Penguin (ペンギン Pengin?)
- Voiced by: Hiroshi Kamiya
An Emperor Penguin and a frequent customer of the café and friend of Polar Bear who generally orders a cafe mocha. He generally serves as the tsukkomi to the antics of Polar Bear and Panda. He has a crush on another penguin named Penko, and eventually upon learning that Penko has other six sisters identical to her, he ends up dating them all.
- Voiced by: Sayuri Yahagi
A female penguin who works at a bakery near the Polar Bear's Cafe and Penguin's love interest. However, when Penguin finally confesses, it turns out that Penko is only one among seven identical sisters taking shifts at the bakery. Aside Penko, the other six are called Penmi, Penno, Penna, Penka, Penuelle and Penjolina. Somehow Penguin started dating all seven at once, although he has a hard time dealing with them as he is unable to differentiate each one from the others.
Animals who were turned down
Badger (?? ??)
- Voiced by: ???
First job applicant.
Tortoise (ゾウガメ Zōgame?)
- Voiced by: Takayuki Kondou
Third job applicant. A Galapagos Tortoise who is a regular at the cafe. Has a very slow speech and pace.
Mandrill (マンドリル Mandoriru?)
- Voiced by: Yousuke Itou
Third job applicant. A mandrill who works at the zoo and visits the cafe.
Anteater (コアリクイ Koarikui?)
- Voiced by: Yuuki Fujiwara
Fourth job applicant. A tamandua who works at the zoo and occasionally visits the cafe.
Fifth reject. See #Panda.
Sloth (ナマケモノ Namakemono?)
- Voiced by: Kishō Taniyama
Unintentional sixth applicant. A three-toed sloth who lives in the café's outskirts. True to his character, he has a very slow pace and speech.
- Voiced by: Aya Endo
A human girl who works at the Polar Bear's Cafe.
- Voiced by: Wataru Hatano
The panda caretaker at the zoo Panda works at. Although he is quite popular with the animals at the zoo, he doesn't have as much luck getting the attention of women. He has a crush on Sasako.
Rintaro Hayashi (林 厘太郎 Hayashi Rintarō?)
- Voiced by: Tokuyoshi Kawashima
A flower shop owner who is nicknamed Rin-Rin (リンリン?) and is incredibly fond of Panda. Although he is considered attractive by many female customers, Panda seems to not be interested in him.
- Voiced by: Kōkō Kondō
One of the workers at the zoo Panda works at. He is Handa's superior.
- Voiced by: Hiro Shimono
A visitor of the café who becomes so moved by the taste of its black coffee that he decides to study under a Tree Kangaroo to learn how to roast coffee beans.