Harlequin is easily the most famous romance only publisher out there. In fact, their name was synonymous with romance novel when I was growing up. They have wide distribution, from grocery stores to bookstores. They are everywhere.
Most of the famous romance writers got their start at Harlequin. They were acquired by Harper Collins a number of years ago.
Their submission process is very user friendly. First you create one account, with that one account you can submit to any of their divisions. After creating an account you fill out a form, upload a synopsis, and a manuscript. If your manuscript is rejected from one division you can always submit it to another.
Each division has a different focus, different editors, and different guidelines. So everything from the length of the manuscript to the content has to match the guidelines for that division. The divisions operate very separately from one another, many are not geographically close and some are located in Canada and some in the states.
Harlequin has so many divisions that focus on different subgenres in romance that it might take you a while just to figure out what might be the best fit for your manuscript. Different divisions are open to different heat levels. Heat levels in the context of romance novels is a scale that measures the amount of romantic/sexual details allowed in that particular division’s books.
Different divisions focus on publishing everything from medical romance novels to paranormal romance novels, to Christian romance suspense novels to Westerns. Be sure to read up on all the divisions to make sure you are submitting to the one that fits your work the best.
Harlequin has a reputation for having contracts that are unfavorable to authors, particularly in the past. They were successfully sued recently by a group of authors over contract issues. However the situation seems to have improved somewhat since their acquisition by Harper Collins.
To learn more visit their main website here. You can also visit their index of divisions and submission guidelines here.