The most common and most likely answer to this crossword clue is the 6 plus 6 letter word DONALD SINDEN
I've seen this crossword clue in Financial Times
D
O
N
A
L
D
S
I
N
D
E
N
Buddy explains!
The straight part
We know that "starred in Two’s Company and Never the Twain" is the straight/definition part of the clue. The straight part is often a synonym or definition, in this case starred in two’s company and never the twain = donald sinden.The cryptic/wordplay part
In cryptic crossword there's often an wordplay/cryptic part as well.This part involves a more complex hint, such as an anagram, homophone, hidden word, etc.
Sadly, We don't have an explanation for this specific crossword clue yet.