Walker signed the measure Monday at Blackhawk Technical College in Janesville.
The money will go toward a series of grants to help eliminate technical college waiting lists for high-demand fields, help high school students get job training for high-demand jobs and help people with disabilities find work.
The $35.4 million for the grants comes from a nearly $1 billion state budget surplus. The Assembly on Tuesday is scheduled to approve a half billion dollar property and income tax cut proposal that taps the majority of the surplus.
The worker training proposal found broad bipartisan support in the Legislature.