So I was just reading your pros and cons to using Illustrator vs Photoshop and thought I'd toss in my 2 cents. As DHB mentioned you can also use the Pen tool in Photoshop to achieve very similar lines as those you would get in Illustrator. But what I'd like to bring to you attention is that there are a few inherent issues with using these tools. For certain things drawing by hand can add life to a drawing. The tiny imperfections can make objects appear more organic rather than sterile and perfect. If you look at a lot of drawings and paintings up close, even by professionals, there are tons of imperfections. But most viewers don't examine paintings or drawings very closely. They stand back and take the entire picture in. It's good to pursue perfection, but it's important to realize that there isn't very much in the world that is actually perfect.
If you want to draw better lines without using the pen tool or Illustrator there are a couple things you can do. First and foremost would be to actually practice drawing lines free hand. As you may have read, drawing nice smooth lines usually come from drawing using your whole arm rather than just your wrist. This can be difficult to do if you have a tablet that is small as you run out of space rather quickly. But this is where practicing with traditional mediums, ie pen and paper, can come in handy.
Here's a nice video that describes some of this. (About 7:50 into the video is where he starts to describe the techniques if you want to skip through the intro stuff) Another nice trick you can do in is to work at high resolution and then reduce the size. Many line imperfections magically disappear when you do this.
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