Because the wireless network picker in Windows 8.1 doesn't show ad-hoc networks, connecting must be done by hand.
To see all networks in range, including ad-hoc, run this command in command shell (cmd.exe):
netsh wlan show networks
SETUP
This must be done once per network.
go to "Network and Sharing Center"
click "Set up a new connection or network"
double click "Manually connect to a wireless network"
enter the SSID of the ad-hoc network (as shown by "netsh wlan show networks") into the "Network name" field
configure security settings accordingly
uncheck "Start this connection automatically" (important)
click "Next", then "Close"
Run this command (important):
netsh wlan set profileparameter <ssid> connectiontype=ibss
Replace with the SSID of your network.
CONNECT
After setting up, run this command whenever you want to connect:
netsh wlan connect <ssid>
Replace with the SSID of your network.
Hovering over WiFi icon in system tray will show the name of the network that you are currently connected to, even if it's an ad-hoc network (the network picker will not show it if it's ad-hoc). The name is also visible in "Network and Sharing Center" window.
DISCONNECT
To disconnect from the ad-hoc network: connect to a different network, turn off wifi, or run this command:
netsh wlan disconnect
CLEANUP
To remove the network profile from Windows, run this command:
netsh wlan delete profile <ssid>
Replace with the SSID of your network.
Is it only when 2nd PC is connected? Or even when nothing is connected Win8.1 can't see it? – Darius – 2013-12-04T07:30:00.747
Regardless of the state the second PC is in, the third one does not see the ad-hoc network. – wonton – 2013-12-05T18:44:45.440