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Bubbles that are the same size will always join at a 120 degree angle because it is the most effective way of reducing the pressure on the bubble. Therefore only 3 bubbles can join at once because there is 360 degrees in a circle and 120 times 3 equals 360. Even in complex structures of bubbles made from foam only 3 will join together.
References
E-how
How stuff Works
Bubbles are made when soap forms a thin film on a surface, e.g - the end of a bubble wand. As air fills the shape (blowing) is forms into a sphere. This is because the film is stretching and so the surface tension is increasing to reduce the surface tension onto the bubble it forms into a sphere because it has the least surface pressure of all shapes.
References-
The Science Bubble,
About.com