I had the same issue on Ubuntu 14.04 and none of proposed workarounds
helped.

The way I was able to solve it was by manually restarting NetworkManager:
1) open terminal
2) type in: sudo stop network-manager
3) type in: sudo NetworkManager
And that is it! Afterwards I was able to normally connect to WiFi even after 
restarting Ubuntu. Hope it helps and good luck!

P.S. If restarting didnt help, before that I was also unsuccessfully
trying to kill NetworkManager by its PID (it relaunches automatically),
maybe it had some impact. I cant really reproduce the bug because it
disappeared after restarting NetworkManager.

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You received this bug notification because you are a member of Desktop
Packages, which is subscribed to network-manager in Ubuntu.
https://bugs.launchpad.net/bugs/1104476

Title:
  Network manager cannot connect to WPA2/PEAP/MSCHAPv2 network without
  CA_Certificate

Status in NetworkManager:
  Fix Released
Status in Release Notes for Ubuntu:
  Fix Released
Status in “network-manager” package in Ubuntu:
  Triaged
Status in Gentoo Linux:
  Fix Released
Status in “network-manager” package in openSUSE:
  Confirmed

Bug description:
  === Release Notes Text ===

  When connecting to MPA2/PEAP/MSCHAPv2 wifi networks which do not have
  a CA Certificate network manager may incorrectly mark the CA
  certificate as needing verification and fail that verification.  See
  the bug for workarounds.

  ===

  I can connect to Eduroam in 12.10 and any other previous release, but
  not in 13.04. I checked, my name and password are correct, all
  settings are the same as in 12.10.

  Network properties:

  security: WPA - WPA2 enterprise
  authentication: protected EAP (PEAP)
  CA certificate: none
  PEAP version: automatic
  inner autentication: MSCHAPv2
  username: (required)
  password: (required)

  ProblemType: Bug
  DistroRelease: Ubuntu 13.04
  Package: network-manager 0.9.6.0+git201301021750.e78c3e8-0ubuntu3
  ProcVersionSignature: Ubuntu 3.8.0-1.5-generic 3.8.0-rc4
  Uname: Linux 3.8.0-1-generic i686
  ApportVersion: 2.8-0ubuntu2
  Architecture: i386
  CasperVersion: 1.330
  Date: Thu Jan 24 21:32:25 2013
  IfupdownConfig:
   # interfaces(5) file used by ifup(8) and ifdown(8)
   auto lo
   iface lo inet loopback
  IpRoute:
   default via 192.168.43.1 dev wlan0  proto static
   169.254.0.0/16 dev wlan0  scope link  metric 1000
   192.168.43.0/24 dev wlan0  proto kernel  scope link  src 192.168.43.149  
metric 9
  LiveMediaBuild: Ubuntu 13.04 "Raring Ringtail" - Alpha i386 (20130123)
  MarkForUpload: True
  NetworkManager.state:
   [main]
   NetworkingEnabled=true
   WirelessEnabled=true
   WWANEnabled=true
   WimaxEnabled=true
  ProcEnviron:
   PATH=(custom, no user)
   XDG_RUNTIME_DIR=<set>
   LANG=en_US.UTF-8
   SHELL=/bin/bash
  SourcePackage: network-manager
  UpgradeStatus: No upgrade log present (probably fresh install)
  nmcli-con:
   NAME                      UUID                                   TYPE        
      TIMESTAMP    TIMESTAMP-REAL                     AUTOCONNECT   READONLY   
DBUS-PATH
   AndroidAP                 978da457-563b-4c59-a894-45eb0f74fcb7   
802-11-wireless   1359063171   Thu 24 Jan 2013 09:32:51 PM UTC    yes           
no         /org/freedesktop/NetworkManager/Settings/2
   Wired connection 1        6703fabc-9519-49bd-a4af-45fbfb7d660e   
802-3-ethernet    1359062570   Thu 24 Jan 2013 09:22:50 PM UTC    yes           
no         /org/freedesktop/NetworkManager/Settings/1
   eduroam                   00f69a95-4a1b-436c-b462-a284f45fbaa1   
802-11-wireless   1359063171   Thu 24 Jan 2013 09:32:51 PM UTC    yes           
no         /org/freedesktop/NetworkManager/Settings/0
  nmcli-dev:
   DEVICE     TYPE              STATE         DBUS-PATH
   wlan0      802-11-wireless   connected     
/org/freedesktop/NetworkManager/Devices/1
   eth0       802-3-ethernet    unavailable   
/org/freedesktop/NetworkManager/Devices/0
  nmcli-nm:
   RUNNING         VERSION    STATE           NET-ENABLED   WIFI-HARDWARE   
WIFI       WWAN-HARDWARE   WWAN
   running         0.9.7.0    connected       enabled       enabled         
enabled    enabled         disabled

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