You can use if a visitor to your site contact you of course if you are at the pc, or you have one of that phones with internet connextion, I think may work too.
And since you know when you have visitors on the site, if they visit say few pages, like product page and after your contact or about us page, I would contact them, a small chat window will pop up on theyr screen and you can ask if they need any help, depending in what you are selling work very well.
Also for returning visitors, wondering around in your site, I would contact them, too.
That works very well if you sell handmade products or anything that you can do custom for them.
Usually people visit a product page, but the product is not just exactly how they like, but if you offer a custom modification, they will happily buy.
I made 4-400 hundreds deals tru the chat in the last week, that probabily I would have missed if I had no chat on the site. talked to the visitor and had the money in my paypal in 20 minutes.
I use livezilla, but also woopra has a free version untill I think 30000 page view a month or something on the lines.
I reread your post, yes I think for a service too will be certanly worth, and also give some sense of professionality, behind it, can also say that is the secretary chatting or any other figure in your company, or live friendly how I do and say that I am the actual artisan making the products, that because in this area, people want to talk with the actual person doing the job, that can really understand what they want.