Ash might meet some lone Pokémon trainers. These trainers could be on their own quests, similar to Ash's. They might have unique Pokémon or training methods that Ash can learn from.
He might meet some local Sinnoh trainers who are experts in training specific types of Pokémon, like a trainer who specializes in ice - type Pokémon in the colder regions of Sinnoh.
There might be a young and inexperienced trainer who is lost. Ash, being the more experienced one, decides to help the trainer find their way. This new character could look up to Ash and in the process, Ash learns more about himself as a role model. It would be an interesting dynamic as Ash is usually the one being guided by his friends.
There could be a wise old hermit who lives in a secluded forest that Ash meets during his solo travels. This hermit might have a deep knowledge of Pokémon lore and give Ash some valuable advice.
He might meet Serena again. Since he has been to Alola and now travels to Kalos, their reunion could be an interesting plot point.
He could meet Serena, who might be his travel companion or a friendly rival. Also, Clemont and Bonnie are likely characters he'd encounter. They could help Ash with his journey in Kalos, like Clemont with his inventions and Bonnie with her cheerful nature.
Lillie is a likely character. She could befriend Ash and they might go on Pokémon adventures together. She has her own story and growth in the Alola region, and interacting with Ash could add more depth to both of their characters. Also, Ash might meet the Trial Captains like Mallow or Sophocles. They could challenge Ash in different ways and teach him about the island challenges.
There could be a lone traveler who Ash meets while he is alone. This traveler might have a unique way of training Pokemon that Ash has never seen before and could teach him some new tricks.
Ash might meet a strict teacher who has no idea about Pokémon at first but gradually becomes interested in them. He could also meet a rival in school who challenges him not only in academics but also in Pokémon battles.
He might meet an old Pokémon expert who gives him tips on hatching the egg.
He might meet new Pokémon trainers in Alola. Maybe some young kids who are just starting their own Pokémon journey.