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Use DbiAddAlias function with necessary parameters.
Example shows adding STANDARD alias.

uses  DBIProcs, DBITypes;
...
procedure TForm1.Button3Click(Sender: TObject);
var
  AliasName, AliasPath: string;
begin
  AliasName:='TESTAlias2';
  AliasPath:='PATH:C:\Tools';
  Check(
    DbiAddAlias(
      nil, 
      PChar(AliasName), 
      nil, 
      PChar(AliasPath), 
      True));
end;

Related topics

Get directory from BDE-alias
Copy and delete table
Create DB file at runtime

For more

BDE Online Reference

Download source