As I understand it, both tetra ethyl lead and ethyl alcohol are anti-knock agents.

Lead was used because it was cheaper.

https://en.wikipedia.org/wiki/Antiknock_agent

Ethanol has other downsides regarding corrosion and reacting with various organic and organic-ish (read: rubber) components. Those were bigger problems back then because everything was carbureted and they didn't have modern plastics.

Ethanol on its own is an anti knock agent. E85 is RON 105 for instance.