According to Mundo Deportivo, Rodri has made 99 La Liga appearances so far. If he plays against Valencia, he will reach the milestone of 100 La Liga appearances in his career.

After returning to the La Liga stage for only four rounds, Rodri is already close to achieving this milestone. If Flick gives him playing time, whether as a starter or a substitute, the Madrid midfielder will update his La Liga appearance record after seven Premier League seasons with Manchester City. His 100 La Liga appearances will include his spells at Villarreal (three years) and Atletico Madrid (one year).
Rodri's La Liga career began at Villarreal: he made 3 appearances in the 2015-16 season, gradually established himself with 23 appearances in the 2016-17 season, and reached his personal single-season high of 37 appearances in the 2017-18 season, for a total of 63 matches. As an Atletico Madrid player, he played 34 league matches. After joining Barcelona, he appeared twice in the first three league rounds, against Athletic Club and Rayo Vallecano respectively, with both matches taking place at Spotify Camp Nou. His La Liga appearance tally has now reached 99.
In this match, Rodri will face Valencia's midfield core Javi Guerra (23 years old). Barcelona have shown interest in him on several occasions, most recently this summer, although the contact was limited to gathering information. Deco appreciates Javi Guerra, but the opportunity to sign Rodri means Barcelona cannot launch any further pursuit.