Story related, unmissable.
Defeat the S-02 boss battle in Chapter 5: Smythe Strikes Back to unlock this trophy.
The first phase of this boss will require you to web shoot the blue fan on its neck in order to expose a weak point. Do this, and then the S-02 will rush at you. Press when prompted in order to dodge, and then web rush with the weak point in its back. Repeat this three times with the three spots on its neck, and you will progress to the second stage. Beware of the energy laser during the latter parts of this first stage, which will deal a lot of damage in one go.
You will now be fighting the robot on the roof of Oscorp. Dodge the tentacles with and keep web shooting the eyes with in order to blind it. Once you’ve webbed it enough, it will smash its tentacles into the building, and you will be able to web rush its face with . Now it will use a sweeping laser attack which you will need to jump over whilst continuing your webbing barrage. After the second web rush to its face, the robot will use both tentacles and lasers, but persevere and a final web rush to the face will finish the boss off. Complete the final quicktime event wherein you web an antenna into the creature’s face, and you will finish this boss.