Use zipAll:
scala> val l1 = List(1,2,3)
l1: List[Int] = List(1, 2, 3)
scala> val l2 = List("a","b")
l2: List[String] = List(a, b)
scala> l1.zipAll(l2,0,".")
res0: List[(Int, String)] = List((1,a), (2,b), (3,.))
If you want to use the same default value for the first and second seq:
scala> def zipLongest[T](xs:Seq[T], ys:Seq[T], default:T) = xs.zipAll(ys, default, default)
zipLongest: [T](xs: Seq[T], ys: Seq[T], default: T)Seq[(T, T)]
scala> val l3 = List(4,5,6,7)
l3: List[Int] = List(4, 5, 6, 7)
scala> zipLongest(l1,l3,0)
res1: Seq[(Int, Int)] = List((1,4), (2,5), (3,6), (0,7))