It is a great option where suitable. Especially as the upgrade options go all the way up the database scale with little effort. By this I mean that it will be the same flavour of SQL and as a subset of other editions of SQL Server the schema (including SQL code) is supported without change by default.

The physical migration of data is a different matter as well as coordination with other systems if there is a near zero sized downtime allowed. But this surely isn't any worse than for any other migration possibilities e.g. OracleXE to Oracle 11G.