1. Draw your line using the pen tool.

draw-your-line

2. Open the Window > Stroke panel.

window-stroke-panel

If you don’t see the arrowhead section try toggling the ‘Show Options’ by hitting the little arrow with squiggly lines.

squiggle-line-options

show-options

3. Add your arrowheads.

add-arrow-heads

arrowheads

http://luanneseymour.wordpress.com/2012/10/30/creating-arrows-and-arrowheads-in-illustrator-cs6/

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