Easily the most obvious choice imo with him on the cusp of the NHL goal record, he probably won't get it next season but following that story is one of the greatest marketing schemes out there of a NHL tv show.
Alternatively if the NHL/Amazon brings this idea back for the 2025-206 season then have the Ovi episode there and have him break the goal record during filming.

If you can't tell from the user name, I'm a Habs fan so this pains me, but with the Leafs having the biggest market in the game we're almost guaranteed a leafs centric episode, and we'll probably be following this mustachioed idiot for an hour of not ad free television.

Another pretty obvious one, Bedsy is a superstar, not using him from a marketing perspective is idiotic. Unfortunate this show is a year removed from his rookie year but following his season is something a lot of fans of the game, not just Chicago fans, would really enjoy seeing.

From my understanding of the format of the show there will be 10-12 episodes each following a single player.
I think it would be really cool to have an entire episode centered around all three Hughes brothers, with a large portion of the episode being centered around the Devils/Canucks games next year.
If not either Jack or Quinn could probably carry an episode all by themselves, I just think it's cooler to play off the sibling connection.

^Read above^

If I had to pick a single goalie to get his own episode I would pick Flower, because obviously. But we don't know where he'll be next year so Igor and the Rangers would be another really good story to follow, plus the third biggest market in the NHL, plus the consistently competitive team could make for just a good general episode of NHL as television as the Rangers try and make it work another year, kinda an episode following a team that's locked into the cup push.

He's Sidney Crosby, need I say more?

In all seriousness, one of the greatest players of the past two decades, if not the greatest. The only factor I can see leading to Sid the Kid not getting an episode is the state of the Penguins, are they trying to be competitive, are they retooling, etc.
Still, Crosby is Crosby, he'll put up numbers no matter what state the team is in, and in any case the marketing around him would go off. "Crosby's Legacy", "Crosby's Last Run", a dozen things a tv show could do with Crosby being the icon to the game that he is.

The NHL's best defenceman, hopefully not a statement that will lead to any disagreement in the comments. Will be (Probably) 2 years removed from a cup win next season and trying to get back there this could be an episode just following the Avs trying to compete for the cup seen through the focus of Makar being the best defenceman in the league.

One of the league's most marketable players, very dependent on him coming back from injury on time and coming back ready to put up good numbers. Also probably dependant on the trade rumors (Although I doubt he's moved). Has enough personality to carry an episode following the abysmal season the ducks are projecting to have next year.

The games best player, kinda a foregone conclusion he probably get's an episode, even if it's probably just going to be about how he's the best player in the league. I think it'll probably happen but not the episode I'd look most forward to.

Another instance of big market+competitive team=good television.
Now excuse me while I go vomit at the thought of an episode focusing on the rat.

Wouldn't mind an episode following Keller, but also if any Yotes player gets his own episode it will be because Bettman is trying to drum up funding for the dumpster fire of the league to stop playing out of a college arena. Alternatively have an episode focused on the first year of Arizona's relocation, but I doubt that will be ready for next years television slate.

(Habs Fan glazing incoming, you have been warned)
The NHL's second biggest market, it's most dedicated fan base, the future has never looked brighter, and despite still rebuilding Montreal proves night in and night out that we have must watch hockey. Take your pick of the storylines any of these three players could bring to an episode:
The youngest captain of the oldest franchise continues his excellent and consistent career as he try's to push himself to further heights and lead his team into the future.
The young goalscorer who needs to brush off his surgery +1 season and truly establish what he can do at the NHL level as he becomes the Habs top goalscorer for the future.
The young first overall pick with, if anything too much personality for TV. Still trying to establish his place among the NHL's best players as he builds off his breakout season, give us the Slaf episode Amazon I dare you.