The MGMT gene codes for a protein that repairs some kinds of damage to DNA, including the damage made by Temodar.
Methylation silences the gene--that is, turns it off.
So, people with methylated MGMT don't fight against the Temodar damage. In people with unmethylated MGMT, the gene is on, they make the MGMT protein, and so they repair the Temodar damage-- therefore Temodar is less effective in patients with unmethylated MGMT.