Well, Doc, the truth may actually surprise you!
Amazing Spider-Man (Vol. 1) #33
Published: c. December, 1965?
Cover Date: February, 1966
“The Final Chapter!”
Plot: Steve Ditko
Script: Stan Lee
Artist: Steve Ditko
Inker: Steve Ditko
Letterer: Artie Simek
I don’t think any era ever showed the contrast between the Peter and Spider-Man personas as well as the Lee/Ditko run. You really got the sense of an uptight nerd getting the chance to express himself while under a mask. I think the very un-heroic, weedy design Ditko gave Peter really helped with that effect.