Polysiloxane polymers with photoinitiating functionality. The polymers may be obtained by reacting .alpha.-allylbenzoin ethers with a siloxane or polysiloxane containing a plurality of silicon hydride groups. Alternatively, the allylbenzoin ethers may be reacted with a hydrolyzable hydrosilane and further reacted with other hydrolyzable organosilanes or siloxanes to form the polysiloxane with pendant photoinitiating benzoin ether groups. The other hydrolyzable silanes or siloxanes may include photocurable groups to yield self curing polymers. In the same manner, photoinitiating siloxane polymers of the first method may be further polymerized to yield self curing products. The photoinitiating polymers may also be combined with ethylenically unsaturated monomers or other silicones with photocurable groups to yield photocurable compositions.