 Volker was a member of the New York State Assembly in 1973 and 1974.In November 1974, he ran for re-election, but was defeated by Democrat Vincent J. Graber, Sr.

On February 4, 1975, Volker was elected to the New York State Senate, to fill the vacancy caused by the resignation of Thomas F. McGowan.Volker was re-elected several times and remained in the State Senate until 2010, sitting in the 181st, 182nd, 183rd, 184th, 185th, 186th, 187th, 188th, 189th, 190th, 191st, 192nd, 193rd, 194th, 195th, 196th, 197th and 198th New York State Legislatures.