The reaction of dialkyl acetals derived from α,β-unsaturated aldehydes with Grignard reagents using TiCl4in THF afforded the cross coupling products, allyl ethers, in high yields. The TiCl4-promoted reaction of alkyl 2,4-dichlorophenyl acetals, synthesized from 3,4-dihydro-2H-pyran or ethyl vinyl ether and 2,4-dichlorophenol, with Grignard reagents in THF at low temperature afforded the corresponding unsymmetrical ethers in high yields. When alkyl 2,4-dichlorophenyl acetals, synthesized from aromatic aldehyde or vinyl ethers and 2,4-dichlorophenol, were treated with Grignard reagents in benzene or toluene at room temperature in the absence of TiCl4, the cross coupling reaction took place and the corresponding ethers were isolated in good yields.