Assuming that you have machine A and B in a Windows workgroup. From machine A you want to make remote connection to machine B.
For PowerShell Remoting to work in a workgroup environment, on both machine A & B, you must first configure your network as a private network, then you must configure the TrustedHosts setting so they will trust each other.
Machine A
1. Run Windows PowerShell as administrator
2. In the PowerShell console, run the following cmdlets
Set-Item wsman:\localhost\client\trustedhosts * Restart-Service WinRM WINRM quickconfig
Machine B
1. Run Windows PowerShell as administrator
2. In the PowerShell console, run the following cmdlets
Set-Item wsman:\localhost\client\trustedhosts * Restart-Service WinRM WINRM quickconfig
3. In the PowerShell console, run the cmdlet "Enable-PSRemoting -Force"