Thisarticle investigates a decode-and-forward (DF) relay-aided hybrid optical wireless/radio frequency (OW/RF) network. The OW subsystem exploits simultaneous transfer of energy and information to increase the system’s lifespan. The end-to-end signal-to-noise ratio statistics are derived using the optical energy transfer at the DF relay. For the proposed DF relay-aided hybrid OW/RF system, Malaga ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\mathcal {M}$</tex-math></inline-formula> )-distribution with non-zero boresight pointing/misalignment error is considered to model the OW channel, and Nakagami- <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$m$</tex-math></inline-formula> model is assumed for the RF channel. In particular, analytical expressions of outage probability (OP), average bit error rate (BER), ergodic capacity, and effective capacity are derived in terms of Meijer’s G-function. To gain additional insights, we also derive the asymptotic expressions of average BER, OP, and effective capacity and estimate the diversity order mathematically. The impact of various system and channel parameters like dc bias, turbulence, weather conditions, and visibility is explored on the system performance. Through numerical results, we show that the proposed DF relay-aided and simultaneous lightwave information and power transfer (SLIPT) -enabled hybrid OW/RF system surpasses its amplify-and-forward-based counterpart. The superiority of the proposed system over non-energy harvesting (EH) and RF-EH-based hybrid OW/RF system is also shown. The analytical formulations are validated with the Monte-Carlo simulations.