Create a Multiple colour glowing Leter in Photoshop - Basic tutorial

1.  Select a New Layer > Fill it with White Colour ( Ctrl + Backspace {Forground} OR Alt + Backspace {Background}.

2.  Select Brush Tool ( Size*= 60px, Hardness= 0% ).

3.  Select Pen Tool > draw a letter using it > Right Click > Stroke Path ( Tool= Brush Tool, Deselect=     Simulate Pressure) > Ok.

          

     To draw Another letter; press 'Ctrl' and make a Click on the white page > Start drawing > Right Click > Stroke Sub path > Ok.

     Do the same steps for All  Letters. Press 'Delete' for removing the path of Pen Tool.

4.   Add a 'New Layer' on Top > Select 'Brush Tool (Size*= 200px, Hardness= 0%) > Select different Colours and paint on different Areas. Change the 'Blending mode' to Overlay*.

 You can also use Blending Mode= color, divide, lighten color for different looks.

Final Image

* you can use different values for better effects.