If you want to store the value in a variable use something like below
variable currDate varchar2(100);
exec :currDate:=to_char(SYSDATE, 'DD/MM/YYYY');
select :currDate from dual;
:CURRDATE
----------
13/05/2014
Or you can use anonymous pl/sql block to do this
set serveroutput on
declare
currDate varchar2(100);
begin
SELECT to_char(SYSDATE, 'DD/MM/YYYY') into currDate FROM DUAL;
dbms_output.put_line(currDate);
end;
/