- Upon leaving EastEnders (1985) in 2007 he enrolled at the Central School of Speech and Drama in order to refresh his skills.
- Learned his trade at Anna Scher Theatre School along with Natalie Cassidy, who would later play his wife Sonia Fowler in EastEnders (1985).
- Turned down the chance to replace Daniel Radcliffe in the West End revival of "Eqqus" (2007).
- Was a friend and a fan of singer Amy Winehouse.
- Was replaced by James Bye in the role of Martin Fowler on EastEnders (1985) in December 2014.
- Is the twin brother of Antoinette Alexandrou.
- Was in a relationship with Kara Tointon (April 2006-November 2007).
- Was unable to attend the wedding of former EastEnders (1985) screen mother Wendy Richard to John Burns in October 2008 as he was heavily involved in the stage production of "All Quiet On The Western Front".
- James' first major TV role was having the part of Martin Fowler in the soap EastEnders (1985). In 1999 he appeared as Grant in the short film 'Blessed Burden'.
- Appeared in the play "The Homecoming" for BBC Radio 3 (2007).
- His interests include basketball, boxing, football and playing the guitar.
- Attended Chingford Foundation School in Waltham Forest.
- His father is Greek and his mother is English.
- Ranked #25 in the 100 Greatest EastEnders (1985) Characters of All Time for his performance as Martin Fowler (2010).
- Ranked #30 in The 100 Greatest EastEnders (1985) Characters of All Time for his performance as Martin Fowler (2015).
- As of 2018 he is the 8th-longest serving actor in the history of EastEnders (1985) (tied with Bill Treacher, Derek Martin and Dean Gaffney, and behind only Adam Woodyatt, Steve McFadden, Perry Fenwick, Sid Owen, Rudolph Walker, a tied Mike Reid and Todd Carty, and John Bardon), having played the character Martin Fowler for 11 years (from 1996 until 2007).
- Has one niece, Darcey (b. January 2016), via sister Antoinette Alexandrou.
- Has been in a relationship with actress Celine Arden since 2012.
- Son of Alekos (b. 1962) and Deborah (née Tovee) Alexandrou (b. 1958).
- Maternal grandson of James (1922-1993) and Eileen (née Peck) Tovee (1929-1961).
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