The telecoms firm claims the service will allow people to make calls with a higher quality and more reliability than "unmanaged VoIP services" from the user’s home, office, corporate or public Wi-Fi.
Calls will be accessible via the phone’s dialler in a development that removes the need for an app, while SMS services will also be made available through Wi-Fi.
The trial will launch this autumn and is aimed to allow people to make calls when they have no mobile network coverage.
Fotis Karonis, chief technology officer at EE, said: "The customer experience is seamless because it’s the same as making a network call and uses the normal call interface of the handset.
"This is a major part of our strategy to invest in giving customers the ability to make a call wherever they are, and we’re confident that this service can make a big difference to people in homes and large offices across the country, especially in the most rural areas, that don’t have mobile coverage."
A trial of allowing VoIP calls over 4G will begin in 2014 with plans for a full commercial launch next year, when EE claims its 4G network coverage will be accessible to 90% of the population.