Two independent efficient photoredox catalytic approaches have been established for alkoxymethylation of electron deficient alkenes employing aryl silyl ether as the suitable coupling partners. In this reaction, the in situ generated alkoxymethyl radical, obtained by the photocatalytic desilylative single electron oxidation of α-silyl ether, coupled with electron deficient aryl/alkyl alkenes to install a new C-C bond. Fukuzumi’s catalyst (Acr⁺-Mes) and Ru(bpz)₃(PF₆)₂ are being found as the suitable catalysts for the oxidation of TMS-modified ether under visible light photocatalytic SET process. In this protocol, both catalytic conditions are compatible with a wide range of substrates scope, in terms of α-silyl ethers or alkene derivatives. The mechanistic study supports the radical pathway for this reaction mechanism. Furthermore, the synthesized ether compounds were subjected to various reactions to produce mono-carboxylic acid, γ-lactone and Suzuki coupling products.