The approved solution does create unique IDs but on first glance they look identical, only the first few characters differ.
If you want visibly different keys, try this:
update CityPopCountry set id = (select md5(UUID()));
MySQL [imran@lenovo] {world}> select city, id from CityPopCountry limit 10;
+------------------------+----------------------------------+
| city | id |
+------------------------+----------------------------------+
| A Coruña (La Coruña) | c9f294a986a1a14f0fe68467769feec7 |
| Aachen | d6172223a472bdc5f25871427ba64e46 |
| Aalborg | 8d11bc300f203eb9cb7da7cb9204aa8f |
| Aba | 98aeeec8aa81a4064113764864114a99 |
| Abadan | 7aafe6bfe44b338f99021cbd24096302 |
| Abaetetuba | 9dd331c21b983c3a68d00ef6e5852bb5 |
| Abakan | e2206290ce91574bc26d0443ef50fc05 |
| Abbotsford | 50ca17be25d1d5c2ac6760e179b7fd15 |
| Abeokuta | ab026fa6238e2ab7ee0d76a1351f116f |
| Aberdeen | d85eef763393862e5fe318ca652eb16d |
+------------------------+----------------------------------+
I'm using MySQL Server version: 5.5.40-0+wheezy1 (Debian)