[2][3] Motylev was the runner-up in the 1998 European Junior Chess Championship, won by Levon Aronian.
In 2003, he won the Corsican Open at Bastia, ahead of a strong field including Loek van Wely, Krishnan Sasikiran and Sergei Tiviakov.
[10] In June 2009, he won the 10th Anatoly Karpov International Tournament (pl) (category 18, 2694) in Poikovsky, Russia.
[12] In April 2014, he took clear second place, behind Pavel Eljanov, in the B tournament of the Vugar Gashimov Memorial in Şəmkir, Azerbaijan.
[14] He placed equal first (second on tiebreak) in the 2015 Russian Championship Higher League with 6.5/9 and qualified for the Superfinal.