He Brazil international was handed the punishment on Wednesday after being sent off during Saturda1-0 LaLiga win over Villarreal for pulling the hair of an opponent.
It is a costly ban, depriving Mourinho of one of his star attackers for an important run of league games that includes a Clasico clash with rivals Barcelona, who hold a six-point lead over Real at the summit of the table.
Vinicius started as Mourinho's side pulled off an incredible late comeback to beat Roma 4-3 in the Champions League, having trailed 3-1 with seven minutes remaining.
But the Portuguese made his feelings clear about how the timing of the announcement had disrupted preparations in a post-match press conference.
Mourinho said: "Do you think it's normal that a player from a Spanish team, who has to play a match that is also important for Spanish football, that two hours before the match a player knows he's been given a four-match suspension?
"Couldn't they do it now? Couldn't they do it tomorrow morning? Do we have to come by bus and almost arrive at the stadium when we find out Vinicius has a four-match suspension?"
Mourinho added: "They do things shamelessly now. The cat is out of the bag now. Two hours before the match, a player must know he has a four-match suspension.
"A Spanish team that has earned three points for Spanish football, for the rankings, for the prestige of Spanish football. You want to kill a player two hours before the match; it doesn't seem normal to me."
SCHEDULING COMPLAINTS
Mourinho also highlighted his unhappiness with scheduling, with his side set to face AEK Athens in the Greek capital on 4 November, before travelling to Valencia in LaLiga on 7 November.
Asked what the Vinicius ban announcement says, Mourinho replied: "At the very least, a lack of respect.
"Playing in Athens on Wednesday night, arriving in Madrid probably at 5am, something like that, and then playing Saturday in Valencia, on a weekend that precedes a week of national team matches.
"It makes absolutely no sense, they make you play on Saturday in Valencia, which is an extremely difficult match, it doesn't seem innocent to me.
"The usual excuses, I don't buy them, because this wasn't 25 years ago. The excuses from TV, that it was TV that decided, that it was TV that chose the match for Saturday, I don't buy this anymore. I'm too old to swallow this.
"And this Vinicius story, two hours before a match, knowing that he has a four-match suspension, doesn't deserve comment. Real Madrid fans aren't stupid and I will do everything possible to open people's eyes."
It was a good night for Mourinho on the pitch, as his substitutions turned the game in Real's favour after they were outplayed for much of the game until the closing stages.
Donyell Malen's double had given Roma a 3-1 lead early in the second half, but two of Mourinho's substitutes scored, Endrick and Carlos Espi, and another, Arda Guler, provided two assists in the late rally.
"I'm not going to be a genius and say I had prepared everything for a 3-1 to 4-3 victory, it's not true," Mourinho said.
"But I genuinely thought that in the last 20 minutes I had substitutions I could make, and I had substitutions that could change things."