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Team Captains have their team named after them, and can be chosen to lead the team. They are also playable in the game's story mode.

Image Name Description Team Name Stadium Star Pitch Star Swing Fielding/Running Bat/Glove Pitch Bat Field Run
Mario Super Sluggers - Mario.jpg Mario A 5-tool player who can hit, run, and pitch. Mario Fireballs Mario Stadium Fire Ball Fire Swing Enlarge Right/Right 6/10 7/10 6/10 7/10
MSS Luigi Artwork.png Luigi A 5-tool player who can jump, pitch, and hit. Luigi Knights Luigi's Mansion Tornado Ball Tornado Swing Super Jump Left/Right 6/10 6/10 7/10 7/10
MSS Peach Artwork.png Peach A slap hitter who can pitch the lights out. Peach Monarchs Peach Ice Garden Heart Ball Heart Swing Quick Throw Right/Right 9/10 4/10 8/10 5/10
MSS Daisy Artwork.png Daisy Her amazing glove is her best feature. Daisy Flowers Daisy Cruiser Flower Ball Flower Swing Super Dive Left/Right 7/10 6/10 8/10 5/10
MSS Yoshi Artwork.png Yoshi Top class speed in the field and on base. Yoshi Eggs Yoshi Park Rainbow Ball Rainbow Swing Tongue Catch Left/Right 4/10 4/10 6/10 9/10
Mario Super Sluggers - Birdo.png Birdo A good player who has trouble hitting curves. Birdo Bows None Suction Ball Cannon Sing Suction Catch Right/Right 4/10 8/10 7/10 5/10
MSS Wario Artwork.png Wario Good stamina and a great contact zone. Wario Muscles Wario City Phony Ball Phony Swing Laser Beam Right/Right 5/10 8/10 3/10 4/10
MSS Waluigi Artwork.png Waluigi Charge swings drop power, but increase hits. Waluigi Spitballs None Liar Ball Liar Swing Quick Throw Left/Left 8/10 4/10 8/10 5/10
MSS Donkey Kong Artwork.png Donkey Kong A strong hitter who can also climb walls. DK Wilds DK Jungle Barrel Ball Barrel Swing Clamber Left/Right 6/10 9/10 3/10 2/10
Mario Super Sluggers - Diddy Kong.jpg Diddy Kong His hits and pitches move like crazy! Diddy Monkeys None Banana Ball Banana Swing Clamber Left/Right 5/10 4/10 8/10 6/10
Mario Super Sluggers - Bowser.jpg Bowser His strength and stamina baffles batters! Bowser Monsters Bowser Castle Killer Ball Breath Swing Spin Attack Left/Right 5/10 10/10 3/10 3/10
MSS Bowser Jr Artwork.png Bowser Jr. A pitcher with great ball and bat control! Bowser Jr. Rookies Bowser Jr. Playroom Graffiti Ball Graffiti Swing Spin Attack Right/Left 5/10 7/10 4/10 7/10