An experimental investigation of the binary droplet collision dynamics was conducted, with emphasis on the transition between different collision outcomes. A series of time-resolved photographic images which map all the collision regimes in terms of the collision Weber number and the impact parameter were used to identify the controlling factors for different outcomes. The effects of liquid and gas properties were studied by conducting experiments with both water and hydrocarbon droplets in environments of different gases (air, nitrogen, helium and ethylene) and pressures, the latter ranging from 0.6 to 12 atm. It is shown that, by varying the density of the gas through its pressure and molecular weight, water and hydrocarbon droplets both exhibit five distinct regimes of collision outcomes, namely (I) coalescence after minor deformation, (II) bouncing, (III) coalescence after substantial deformation, (IV) coalescence followed by separation for near head-on collisions, and (V) coalescence followed by separation for off-centre collisions. The present result therefore extends and unifies previous experimental observations, obtained at one atmosphere air, that regimes II and II do not exist for water droplets. Furthermore, it was found that coalescence of the hydrocarbon droplets is promoted in the presence of gaseous hydrocarbons in the environment, suggesting that coalescence is facilitated when the environment contains vapour of the liquid mass. Collision at high-impact inertia was also studied, and the mechanisms for separation of the coalescence are discussed based on time-resolved collision images. A coalescence/separation criterion defining the transition between regimes III and IV for the head-on collisions was derived and found to agree well with the experimental data.