I got only jagged lines with corners not rounded, especially when the angle of curvature is really small.
This was a problem in Unity 5.4 and below. This issue has been fixed in Unity 5.5 and higher after it has LineRenderer
been completely redesigned.
All you have to do is upgrade to Unity 5.5 or higher, and this problem should go away.
There is a new variable called LineRenderer.numCornerVertices
. You can use this to set how smooth your line should be. A value of 5 seems good for this.
There is also another new variable called LineRenderer.numCapVertices
that can be used to determine how smooth the end of the line will be.
This is a screenshot showing between 5.4 and 5.5 changes:

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