The heterogeneous gold-catalyzed cyclization of (o-alkynyl)phenoxy- or N-(o-alkynylphenyl)tolylsulfonamidoacrylates with alcohols has been developed by using an MCM-41-anchored diphenylphosphine-Au(I) complex [MCM-41-Ph2P-AuNTf2] as the catalyst under mild reaction conditions, yielding diverse functionalized benzo[b]oxepines or benzo[b]azepines with good to high yields and excellent diastereoselectivity. This heterogenized gold(I) catalyst exhibits a comparable activity to homogeneous Ph3PAuNTf2 and can be facilely recovered by a simple filtration of the reaction solution and reused more than seven times with almost a consistent catalytic efficiency.