Multiple different versions of Dio appear in the game, reflecting the events of the original story. Although two iterations can be used in 77 Rings Knights Mode, most of his playable variations are exclusive to Dio Mode, a mode where the player follows the story through Dio's perspective.
The first stage of Dio Mode has the player taking control of Dio during his boxing match with Jonathan Joestar. Dio's moves parallel Jonathan's, save for his unique dodging style and automatic counter if he is hit while guarding.
Dio Brando (Boxing)
Left Body Blow
Dashing Right Straight
Dashing Left Body Blow
Ducking & Sway
Available Stages: Dio Mode 01
The second and third Dio Mode fights pit Dio against Erina's bullies and a furious Jonathan respectively. It is implied by the former fight's title, Increase Your Minions! (子分を増やせ！), that Dio impresses the bullies by defeating them, causing them to accompany him to his confrontation with Erina Pendleton.
Dio Brando (Young)
Ducking & Sway
Available Stages: Dio Mode 02, 03
The fourth fight in Dio Mode sees an adult Dio take on Jonathan in an attempt to prevent him from taking George's poisoned medicine. Dio's moveset has changed in the seven years since his last fight: his combo has increased in length, giving him an additional move. In the fifth Dio Mode battle, this version of Dio takes on a vampiric vagrant after using the Stone Mask on him.
Dio Brando (Adult)
Dashing Right Hook
Dashing Left Upper
Sway & Ducking
Available Stages: Dio Mode 04, 05
After becoming a vampire, Dio's moveset changes greatly: Dio can now drain an opponent's health via his Charge Move, his dodge changes once more, and he gains the ability to counter enemy attacks. This form of Dio fights Jonathan with and without his spear in the sixth and seventh Dio Mode fights; the eighth and ninth fights pit him against Jack the Ripper and an onslaught of zombified knights respectively.
Dio Brando (Vampire)
Vampire Back Kick
Available Stages: Dio Mode 06, 07, 08, 09
Dio reaches his most powerful form at Dio Mode's tenth fight, acquiring his signature freezing technique and changing nearly his entire moveset to incorporate it. In addition to his ice-based moves, Dio also unlocks the Space Ripper Stingy Eyes technique. Notably, this version of Dio is the only character to have two different portraits in the same outfit and status.
After defeating the undead Bruford and Tarkus in the tenth Dio Mode fight, Dio faces the three 77 Rings champions in the eleventh, followed by Doobie and Dio's own zombie chimeras in the twelfth; Zeppeli and a hammer-wielding Speedwagon confront Dio in the thirteenth fight, and the threeRippleWarriors fight Dio in the fourteenth. The fifteenth stage of Dio Mode sees Dio engaging in a climactic battle with Jonathan, who is accompanied by Speedwagon. This form of Dio can also be unlocked in 77 Rings Knights Mode.
In the secret alternate version of Chapter 23, Dio grafts his head onto Father Styx's body during his final battle with Jonathan; this version of Dio is identical to his previous form moveset-wise, and is non-playable.
Available Stages: Dio Mode 10, 11, 12, 13, 14, 15
77 Rings Knights Mode: Living Corpses
The sixteenth and final battle in Dio Mode has the player take control of Wang Chan as he holds Dio's head; the two must defeat Jonathan while fighting off Father Styx and two policemen. While holding Dio, Wang Chan's moves are mostly replaced by various forms of Dio's Space Ripper Stingy Eyes. This form of Wang Chan can be unlocked in 77 Rings Knights Mode after Dio Mode is cleared.