They meet when Marcus Pierce was transferred to the Los Angeles Police Department. First Pierce was distant with Chloe all this was part of his plan to finally die. But as Chloe did not allow him to die, he became a little uninterested in her and focused on Lucifer to find a solution by entering into a pact with him but when their pact was canceled because Lucifer wanted Chloe be safe Cain depressing believer can not find any way to die.
Then in "Let Pinhead Sing!", looking at the relationship that Chloe and Lucifer had and also witnessed that Lucifer was injured in the presence of Chloe, he said he wanted to have the same thing as them and he invited himself to the concert of Axara with Chloe who had received the two tickets from Axara.
The day after their appointment, they discuss and Pierce will personally be involved in the investigation on which the Deckerstar Duo will participate since many years ago he participated in a similar case. They end up setting a trap for the killer by simulating a false meeting. Pierce invites Chloe home and they discuss a little, Pierce admits he has long established a wall between him and others but wants to try to make him fall with her.
At the end of this episode Pierce tells the granddaughter of an old romance that he will not be heartbroken because Chloe is only one way to get what he want.