That depends. Most of the affiliate sites I've seen with "live" chat are never online. So you can send them an email which is no better than a contact form. The live chat box is for appearance only.

If someone was actually online most of the time it might help.

Brent

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Live chat works when a visitor can chat w/o having to fill out a form prior to chatting. Also when the chat is staffed 24/7 by live agents it shows prospects your company is always available vs "sorry please leave a message and we'll get back to you"(form fill). I work for a company that offers 24/7 manned live chat and is performance-based. Many of our customers tried a software but weren't able to dedicate the resources to staff it. #'s are alarming on the low end 20% increase in converting website visitors into leads and 42% of our leads are generated after hours (nights and weekends). Yes, live chat will help with conversions and to maximise conversions I would try to staff around the clock.

What types of questions are you looking to answer? Product/Service/Support/Sales?

You can place the trained live chat agents on the website and if you are doing good and no spamming then you do not have to worry.
AS you also know that having chat agents on your website will be the best available hack for you to grow in the market.

I am not expert at affiliate marketing but have designed websites about affiliate marketing. I think it would be beneficial. A study confirmed that sites using live chat increase conversion by 30/40%. I think if you have a great deal of knowledge about the affiliate product you are selling and can answer specific questions about it, it would be beneficial. Why not?

Yes, you can set up a live chat on any websites you want. There are no bindings as far as I know. Even you can redesign, send users private message, banned them. This totally depends on which chatroom are you using. Myself totally depends on ChatWing. And using it over 2 years. Much reliable and effective.