I still remember fighting Psycho Mantis in Metal Gear Solid 1. He would read all your moves before you did them and was literally impossible to beat. He would also talk to you about the games that you had already played by reading your memory card (this was super trippy). The only way to beat him was to unplug your controller and plug it into port two so he couldn't read you moves anymore. It took me and my buddy days to figure it out... This was before Google too, so you couldn't just look it up.
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Gehrman, The First Hunter from Bloodborne... He isn't the hardest boss but he was definately the most frusterating boss I've fought in my life. I was raging hard till I got on this morning and wreckt him and moon with 1 blood vial