I love this idea, but i want to take it a step farther. Make the EX characters alternate possibilities of the same champ. For your Kalista example, shes a spirit of Hatred instead of vengence, which is why she is so much more aggressive. However, for balance, i do think bans on a champ should also ban the ex and vice versa, just so you don't have to ban 2 of the same champ. I have some ideas from this myself.
EX Annie, The Acursed (adult version, doesn't know parents, never got Tibbers)
AP SHort ranged. Only one ranged skill but does punishing damage. Best built as tanky AP. (RoA Rylai's etc.)
Passive: Cursed Flames: Each time Annie casts a spell, she gains a stack of Acursed. Upon reaching 3 stacks, her next ability will empowered.
Q: Dark Touch: Annie throws a powerful fireball in a straight line, dealing magic damage and slowing them. Empowered= This skill now passes through units and stuns the first target hit.
W: No Escape: Annie taps into the fire in her soul, creating a small wall of fire then dragging it to her, dealing damage to enemies hit and dragging them with the skill. (Think of a fan shaped skill, but it starts at the end of the fan then, after a .2 sec delay, pull inwards to Annie) Empowered= This skill catches it's victims aflame, making them take more magic damage over time.
E: Ravageness Aura: The curse lashes out at people naturally, causing magic damage to a nearby enemy unit every few seconds. Activate to explode with power, dealing high magic damage all around you. The passive is off while on CD. Empowered= Nothing hurts like being alone. Annie repeats the skill 2 more times, dealing more damage and heals herself if someone gets hit by all 3 waves.
R: Let It Burn: Intense pain and anger can only stay for so long. Using this ultimate releases a portion of her misery, teleporting to a location then channeling powerful fireballs to nearby targets. Each fire ball does little damage, but are plentiful and increases amount of fireballs with CDR (think of how Lucian ult scales with AS) Annie also heals herself if someone dies, a short short release in never ending pain.
This annie is 100% damage, but has much higher risk with more AoE damage. While classic Annie is good against a target, this one is at home in team fights. Her single target damage is fairly weak, but her area damage is fearsome.
EX Lucian (Senna), The Isle Slayer (Senna is okay, Lucian got captured. Calmer and more calculating. Uses just her pistol until ultimate)
Passive: Final Judgement: When Senna uses an ability, she gains a stack of final judgement, adding 20% more AD to her next basic attack and increasing its range by 50. Stacks up to 5 times. Stacks do NOT give additional stats, but rather allow more autos with these enchantments. (average initial ADC range, without buff)
Q: Lightbound: Senna shoots a bullet of holy energy, striking her chosen target. Then, a line between Senna and the target appears. If any enemy champion is caught between this line, it will disrupt it, stunning her target and the person who breaks it. If the light remains it's whole duration, Senna recovers half the mana cost. (her only point and click, like Lucian Q)
W: Burden of Guilt: Using a powerful holy text, Senna binds an over time effect (magic but with strong base) on the enemy (skill shot style). This DoT builds damage as it is hit by Senna's Autos. If this fully stacks up, the target will take large magic damage at the end of it's duration.
E: Pursuit of Justice: Teleport a short distance, then empower your gun with a special bullet. You next Auto attack will grant you a large bonus to lifesteal (10/20/30/40/50%). Your main survival and only escape, as well as best chase.
R: For Lucian...: Senna pulls out her husband's gun and uses both her gun and his at the same time. Senna now shoots a nearby target as well as her main target. If no one else is around the target, it takes 20% more damage from the attacks. Each gun applies on hit effects. Lasts 4/6/8 seconds. Killing an enemy champion will reduce the remaining CD of this ult by 50%. Assists reduce the CD by 25%.
This version of "Lucian" is a highly tactical AD caster who sets up strong combos for maximized effect, but lacks good damage if not executed right. Her high harass can make her extra annoying to deal with and her Q and Ult help counter Jungle ganks by punishing both the laner and jungle with a stun.
Like these ideas so far? I think we are on to an interesting idea. Maybe they won't be allowed for Ranked play, but my god this would be fun casually.