This is a guide by Adam Burley.

For each character and each series, the first episode/film they appeared in is listed, if indeed they appeared at all for that series. The series included are:
If anyone else has any other information, for example on, the Kirk Alyn serials, or George Reeves films/TV series then please let me know!!
Please note that characters who appeared in more than one Superman production but did not appear in the comics (for example, Eve Teschmacher, who will appear in the eighth season premiere of Smallville and also appeared in the first (1978) Superman film) are not eligible for this list. I am also not currently interested in animated productions (e.g. the 1996-2000 TV series), or productions which did not feature Superman (e.g. the JLA pilot).

"Real" Name (Future) Hero/Villain Name (if applicable) CRF SBY NAS SMV BRF
Bart AllenThe Flash       4x05  
Davis Bloome1Doomsday       8x01  
Kent ClarkBizarro 2 2x06 1x193 6x014  
Johnny CorbenMetallo   2x035 2x10    
Bridgette Crosby        4x01  
Arthur CurryAquaman       5x04  
Morgan Edge  IV6   2x207 3x01  
Vincent Edge      2x058    
Claire Foster        3x05  
Milton FineBrainiac       5x01  
Kyle Griffin9The Prankster     2x04    
Emil HamiltonRuin     2x07 8x12  
John JonesMartian Manhunter       6x0811  
Jor-El  I (2x18)12 1x17 2x22 I
Clark Kent/Kal-ElSuperman I 1x01 1x01 1x01 I
Jonathan Kent  I 1x10 1x01 1x01  
Kara KentSupergirl       7x01  
Martha Kent  I 1x10 1x01 1x01 I
Dinah LanceBlack Canary       7x11  
Lois Lane  I   1x01 4x01 I
Lucy Lane      1x01 4x16  
Sam Lane  I   1x05 4x02  
Lana Lang  I 1x01 3x14 1x01  
Lara-El  I     3x19  
Lex Luthor  I 1x01 1x01 1x01 I
Mikhail MxyzptlkMr. Mxyzptlk   1x16 2x11 4x07  
Non  I        
Jimmy Olsen  I   1x01 6x01 I
Parasite    2x0913   14  
Oliver QueenGreen Arrow       6x02  
Andrea RojasAcrata       5x13  
Pete Ross        1x01  
Maggie Sawyer        2x11  
Winslow SchottToyman   2x2115 2x09    
ShelbyKrypto       4x14  
Victor StoneCyborg       5x15  
Ursa  I        
Perry White  I   1x01 3x05 I
Loretta YorkYellow Peri   2x14      
Zod  I     5x08  
Zor-El        7x06  

Footnotes

1  In the comics, this character has no "real" name, but he is known as "Davis Bloome" on Smallville.
2  Although an evil clone of Superman does appear in Superman III, there is no indication that this clone is similar at all to the traditional character of Bizarro. Interestingly, another evil clone of Superman is created in a deleted scene from Superman IV.
3  The character is not referred to by name, but Lois does say that he is "bizarre", which is a clear reference to Bizarro.
4  Bizarro technically does appear in the season 6 premiere "Zod" (listed here), in his non-corporeal form. He appears in his standard form in the season 6 finale "Phantom".
5  In this version, the character is known as "Roger Corben" rather than "John Corben".
6  In this version, the character is known as "David Warfield".
7  In this version, the character is known as "Bill Church Junior".
8  In this version, the character is known as "Bill Church Senior".
9  In the comics, this character is known as "Oswald Loomis".
10  Martian Manhunter does technically appear in the episode "Static" (listed here), in his non-corporeal form. He appears in his standard form in the episode "Labyrinth" (season 6, episode 12). In this latter episode, he is not referred to by name, except in the deleted scenes, but it is clear that he is the Martian Manhunter.
11  This version of Jor-El turned out to be an impostor, but this was not clear at the end of the episode "Abandon Earth" in which he first appeared.
12  This character is not referred to by name as Parasite, but bears similar characteristics.
13  The character of "Eric Summers" from Smallville is speculated to be Parasite, due to his behaviour during the episode "Leech". However, this method of power transference has also been exhibited in the episode "Wrath" with a different person, and so is not unique to Eric's body (in other words, it could have happened to anyone).
14  In this version, the character is known as Nick Knack.