He is the father of Nalan Yanran, he was extremely disappointed in her when she broke up the engagement without his consent.
He is the grandfather of Nalan Yanran, he was the one who set up the engagement between Xiao Yan and Nalan Yanran. He was also the one trained her when she was small and is quite protective of her even though he is strict when training her.
Xiao Yan is her ex-fiance who broke up with her after beating her in battle. At first they have a bitter relationship that contain a lot of hatred, however Nalan Yanran was in love with Yan Xiao (Xiao Yan's disguise). In the light novel, she has a lot of admiration for the potential and abilities of Yan Xiao and seems to have fallen for him due to his performance in the Grand Alchemist Tournament.
Liu Ling and Nalan Yanran have been friends for a long time. Liu Ling has romantic feelings for Nalan Yanran,even though she does not return his feelings. She has told him that even though he's outstanding, he does not possess the requirements to move her heart.
Yun Yun is her master in Yun Lan Sect, they have a close relationship. As a member of the Misty Cloud Sect, Yanran was not supposed to form relations with a man until she became a Sect Leader, Yun Yun asked her to cancel the marriage agreement between her and Xiao Yan.