5. Helena Bertinelli
Background: The daughter of mob boss Frank Bertinelli, Helena Bertinelli began to amass evidence that would send her father to jail. When key figures in the organization learned of a leak, however, Helena's fiancé was wrongfully executed as the culprit. Michael's death set Helena on a path of destruction. Rather than satisfying her conscience by turning her father in to the authorities as planned, Helena takes on a vigilante role and begins killing his men. Although Oliver forcibly stops her from killing her father, her determination to avenge Michael ultimately leads to Frank's accidental death in a shootout. Appearing first in Season 1's "Muse of Fire," Helena is the first person to deduce Oliver's identity as the Arrow as well as the first individual that Oliver would bring into the Arrow cave without extenuating circumstances. She provided an intriguing parallel to Oliver. Both were perfectly willing to kill as part of personal vendettas against a certain subset in Starling City, and the implications about Oliver's flexible morality needed addressing. Helena would appear three more times, posing a serious threat and leaving an abundance of collateral damage each time.
Motivation To Join: With the all-consuming quest to murder her father with her own hands irrevocably and unsatisfactorily concluded, Helena demonstrated a possible return to her belief of justice over vengeance in a final conversation with Oliver. If Oliver could come back from his Season 1 darkness, why can't she?
Skills: Boasting peak physical condition, remarkable reflexes, mastery over relatively obscure weapons, and a signature crossbow, Helena was a formidable foe...and would make an awesome ally. Able to think on her feet and not constrained by any personal vows, Helena managed to land blows on both Oliver and Sara in hand-to-hand combat.
Availability: Out of the picture. Helena is currently imprisoned for her crime and murder spree. Short of an unlikely acquittal or a prison break, Helena will probably be off limits for a while.