Stormer's right. The 25th Anniversary is basically a "Classics" line. You want new faces and ideas, that's what Joe Vs Cobra, Spy Troops and Valor vs Venom as well as Sigma6 did/tried.

But just for the fun of it, let's try this out.
List of new characters.

2002. JvC.
Dart. Showed up in the DD comic, had bad war experience, had nitemares, never seen again. Fact is, Hasbro lost the rights to a whole bunch of names. Roadblock and Spirit are the best known. Because of the loss of rights, Heavy Duty was used in the place of Roadblock and Dart was created for Spirit. Keep in mind that Scarlet became Agent Scarlet for JvC and Hawk became Gen. Tomahawk for a time. The change in titling the chars is a rights issue.

Cobra CLAWS. I think they showed up in the comic for a panel or two.

Cobra NeoViper. Showed up in the DD comic twice. First time, they were in formation. 2nd time, they got their butts handed to them by Destro. Probably Hasbro's attempt to create a new iconic generic trooper (like the Trooper and Viper) but the mix of gorilla arm and t-crotch most likely killed it's chance to be ultra-ultra cool. The rainbow of colors might have not helped too.

Cobra NeoViper Commander. All troops need leadership. lol. No support in comic or cartoon form.

2003 Spy Troops
Agent Faces. This was, iirc, the era where if a Joe dies in a comic, he's supposed to stay dead. That was ok'd by Hasbro. There was NEVER a list of who could be killed but it was more like, "can I kill so-and-so off" and Hasbro would say either, "yes" or "no". Agent Faces, in other words, was the replacement for Chuckles. I don't remember if he got comic time, but Spy Troops favored him as did Hasbro. *rolls eyes*

Crosshair. A tiny bit part in the DD comic. No time in the cartoons. IIRC, the LowLight name had been lost so Crosshair was created.

Depth Charge. Showed up in comic (iirc), no movies.

Kamakura. Liberal use in the comic and cartoon. DD's creation, Hasbro loves ninja, DD created a winner in Hasbro's eyes. The fans are so-so about the green power ranger.

Rampage. No time in comic or movies.

Red Spot. I don't remember if he showed up in the comic, but sure not in the movies. Replacement for both Flash and Sci-Fi. Nobody understands why Sci-Fi simply wasn't brought into the fold. Unless Red Spot falls under "new character".

Sgt. Hacker. I don't recall him in the comic and no use in the movies. Hacking must be all the rage. Nobody knows why he was made.

Switch Gears. I don't recall if he was in the comic and had no use in the movies. However, he is an excellent candidate to roll in the Patriot Grizzley for the traditionalist types that can't see Wild Bill in a tank. Like me.

Widescope. Short time in the comic, no movie time. Hasbro lost the rights to Shockwave.

Barrel Roll. Time in the comic, none in the movie. The real dynamic is that he has a sister on the team and a brother who has gone bad.

Blackout. Time in the comic, none in the movie. See above.

Burnout. No time in comic or movie. Hasbro says, "Let's create a new 'nok and make people mad for not doing Buzzer!!!"

Claws Commander. Shows up for a couple frames in the comic, no time in movie. Hasbro says, "We love gorilla arms!"

Coil. May have shown up in comic, no show in movies.

Heavy Water. May have shown up in comic, no show in movies. Someone at Hasbro was pregant. *shrug*

Overkill. Short appearance in comic, lotsa love in VvV. Was this an ARAH character?

Pit Viper. No appearance in comic or movie.

Sand Viper. No apperance in comic or movie.

Scalpel. Showed up in DD comic, no movies. Fans wanted a Cobra medic.

2004 Valor vs Venom

Link Talbot. NO time in comic, made for movie.

Hard Drive. No time in comic or movie.

Hi-Tech. No time in comic, loved in movie. Both HD and HT take place of Mainframe.

Ninja Trooper. No time in comic or movie. Hasbro had considered doing a ninja spinoff.

Coil Crusher. No time in comic, in movie. Made for the movie.

Electric Eel. See above.

Neuortoxin. Time in comic, no movie. Made for theme.

RazorClaw. No comic, time in movie. Made for theme.

Snow Wolf. No comic, time in movie. Made for Theme.

Swamp Rat. No comic or movie. Made for theme.

Ven Max. No comic, time in movie. Made for theme.

Rollbar. No comic or movie.

Ghost Bear. No comic or movie.

2005 VvV

Bombstrike. No time in comic or movie. See Barrel Roll.

Slash. No time in comic, time in movie.

Shadow Strike. No time in comic or movie. Made for ninja theme.

Tiger Claw. No time in comic or movie. Made for ninja theme.

2005 DTC

Major Barrage. No time in comic or movie.

Cannonball. No time in comic or movie.

Medi Viper. May have shown up in DD comic, no time in movie. Fans wanted Cobra medic.