Killing NPCs in cinematics is a name of a glitch, otherwise known as "Explosives At Cutscenes", because of it's wide use there and is possible in many levels in the original GoldenEye 007 for N64. There are a number of ways to do so.
Overview[]
NPCs other than Bond himself have completely normal hitpoints in cinematics and can be damaged or killed just like in gameplay. Killing them serves no purpose other than for sheer amusement, though seeing as Natalya Simonova dying is a mission failure condition, the mission will fail if her body vanishes before the cinematic ends.
Methods[]
Two pad control[]
Using one of the control settings which places the fire button on the second joypad will allow the player to fire their gun normally at the middle of the screen during cinematics. This can be used to shoot Natalya at the end of Archives and Baron Samedi at the end of Egyptian.
Explosives[]
All explosives will deal normal damage to NPCs; Proximity Mines and Hand Grenades are best for achieving this. Explosives can be used to kill the guards who take Bond captive at the end of Surface 2, the guards in the boxcar at the end of Depot (causing Bond's model to glitch and point his gun at the ceiling), Mishkin and his men at the end of Statue, Natalya at the end of Bunker 2, Archives and Train and, using a complex system of remote mines up one wall and along the ceiling, Baron Samedi at the end of Egyptian.