First, there are the stories you only get if Peter Parker's not in a romantic relationship, in addition to the stories that are the consequences of a prolonged stretch in which he is not in a romantic relationship.
The Brand New Day period lasted for more than fifty issues before Spider-Man began his relationship with the Black Cat. Part of the impact of "The Big Time" era was based on Peter finding success in his personal life as well as his professional life, after a duration in which things weren't very rosy.
Then, there are the stories you get when he's in a romantic relationship with MJ, but not actually married to her. I posted this elsewhere, so maybe I'm spoiling something published a decade from now.
Peter tells MJ he still loves her and he wants her back, but she's unsure how to react. Later, Mary Jane is threatened by supervillains and Spider-Man saves her. There's a brief moment where she thought that Spidey was dead. They kiss passionately.
Peter & MJ are in a hotel room post-reconciliation, ready to tell their loved ones that they're back together. Except they learn that the video of Spider-Man kissing Mary Jane is in the news. Her agent, never one to miss an opportunity, says that Spider-Man & Mary Jane have had an on/ off relationship for years. Gayle Watson's fiance claims that he & Gayle double-dated Spider-Man & Mary Jane.
Peter & MJ realize that it would be quite suspicious if they announce that they're dating, shortly after she was connected to Spider-Man. With her new notoriety, MJ starts getting all sorts of job offers.
Eventually, the two decide it would just be best if they were to publicly see one another as Spider-Man & Mary Jane. As Peter's friends are oblivious to this, they think it's a bummer that his ex-girlfriend is dating Spider-Man, especially if he mentioned to one of them that he's still in love with her. And he's annoyed that he can't tell them that he's seeing someone, as they keep trying to find a match for him.
A minor supervillain decides to get back at Spider-Man by targeting MJ. He's caught by Doctor Doom, who feels that he owes Spider-Man a favor. Latveria's entry for the Best Foreign film Oscar is footage of the villain starving to death in a reality in which time moves differently. Doom promises that he'll do the same to anyone who targets Spider-Man's girlfriend or her loved ones.
Peter starts pondering whether he even needs a secret identity anymore. And he wonders if he's a better boyfriend to MJ as Spider-Man, than he is as Peter Parker. He's invited to all sorts of social occasions.
Spider-Man & MJ pay a surprise visit to Gayle and her family, who have talked about them often to the news. Gayle's kids likes Spider-Man a lot more than they liked Peter Parker, and Peter realizes that he didn't even know their names. Gayle's fiance ends up being a well-meaning guy, who has been able to put his future stepchildren through college with some embellishments.
At one point Spider-Man & Peter Parker are invited to the same party. Johnny Storm agrees to disguise himself as Spidey, so that more people see Peter & Spider-Man at the same place at the same time. And it may end in fisticuffs between the two, as Johnny starts doing what he can to embarrass Peter/ Spidey.
In a testament to Dan Slott's talent, he also came up with the idea, but he used it as a throwaway gag in the space of three panels in Amazing Spider-Man #552.
There are also stories you only get when MJ's in a relationship with someone else. Peter's in an awkward position when Mary Jane dates a coworker of his at Horizon Labs. Mary Jane dates a good man, who dies after pissing off the wrong people; now it's Peter's turn to comfort her after the loss of a loved one. Mary Jane dates a guy who hates Spider-Man. Mary Jane dates a guy who really likes Spider-Man . Mary Jane is in a stable relationship with someone other than Peter Parker. Mary Jane is in an unstable relationship with someone who hates Peter Parker.
As it became evident that there were a lot of stories that could only be told when Peter Parker and Mary Jane are single, after Spider-Man's unmasking, I started pondering how Marvel could get to that status quo.
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