In episode 189, Zigfried von Schroeder uses this card during his duel against Weevil Underwood and Rex Raptor. He summons two copies via "Ride of the Valkyries". Zigfried then uses the effects of his two "Valkyrie Zweites" to destroy "Insect Queen" and "Black Tyranno". He then uses the effect of one copy of this card to banish "Insect Queen" and make the ATK of this card the same as "Insect Queen's" ATK. Zigfried then uses the effect of the other copy to banish "Black Tyranno" and make the second copy's ATK the same as "Black Tyranno's" ATK. Zigfried then uses all four of his monsters to attack Weevil and Rex directly, winning him the duel.
In episode 190, this caard is shown in Zigfried's hand during his Duel against Joey Wheeler. In the next episode, Zigfried Special Summons this card via the effect of "Ride of the Valkyries". Zigfried then uses the effect of one of his "Valkyrie Zweite" to destroy "Jinzo". Zigfried then uses this card's effect to banish "Jinzo" and make this card's ATK the same as "Jinzo's" ATK. All of Zigfried's monsters then attack directly, but Joey activates "Hyper Refresh" to double his Life Points before Damage Calculation. This allows Joey to survive the direct attacks with 800 Life Points remaining. On Zigfried's End Phase, all of his monsters return to his Deck. Later Zigfried activates "Swan Maiden" to Special Summon this card from his hand. This card then attacks Joey's "Sasuke Samurai", but Joey activates "Silver Dollar" to prevent "Sasuke Samurai" from being destroyed and to nullify the damage he would have taken. Later "Maximum Six" attacks "Valkyrie Brunhilde", but Zigfried decreases the DEF of "Valkyrie Brunhilde" by 1000 in order to prevent its destruction, however Zigfried still takes Battle Damage. "Red-Eyes B. Dragon" then attacks and destroys this card.
In episode 194, Zigfried uses this card during his Duel against Seto Kaiba. He summons this card via "Ride of the Valkyries". Zigfried then activates the effect of "Valkyrie Zweite" to destroy "X-Head Cannon". He then activates this card's effect to banish "X-Head Cannon" and make this card's ATK the same as "X-Head Cannon's" ATK. "Valkyrie Dritte" then gained 100 ATK due to a monster being in the Banished Zone. Zigfried then uses "Valkyire Zweite" to attack directly, but Kaiba activates "Negate Attack" to negate the attack and end the Battle Phase. Zigfried then activates "Mischief of the Time Goddess" to go to the Battle Phase of his next turn. Zigfried then uses "Valkyrie Zweite" to attack directly, but Kaiba activates "Magical Trick Mirror" to activate "Mischief of the Time Goddess" from the Graveyard as his card, allowing Kaiba to go to the Battle Phase of his next turn. Later Zigfried uses this card to attack and destroy "Clone Dragon". In the next episode, Zigfried uses the effect of "Fortune Chariot" to halve the ATK of "Valkyrie Zweite" until the End Phase so that it could attack Kaiba directly. "Valkyrie Zweite" then attacks directly, but Kaiba activates "Attack Guidance Armor" to redirect the attack to this card. Zigfried then activates "Wotan's Judgment" to swap a Spell Card in his hand with the top card of his Deck in order to negate the attack and end the Battle Phase. Later Zigfried Tributes this card and "Valkyrie Zwei" in order to Tribute Summon "Valkyrie Brunhilde".
In the second above-mentioned episode, this card appears within Zigfried's backstory flashback. When Zigfried was testing out the Holographic Duel Monster projection system he had created, he used this card as the test subject. After playing this card, a hologram of the monster then appeared.