A conceptually novel methodology is explored for in situ recycling of nanoparticle catalysts based on transforming a conventional organic/aqueous biphasic system into a Pickering emulsion/organic biphasic system (PEOBS). The suggested PEOBS exists as two phases, with the nanoparticle catalyst “anchored” in the Pickering emulsion phase, but is “continuous” between the organic phase and the continuous phase of the Pickering emulsion. Aqueous hydrogenations are used to evaluate the reaction performances of PEOBS, and the underlying principles of PEOBS are preliminarily elaborated. The unique properties of PEOBS lead to many intriguing findings, which are unlikely to be achieved in the reported biphasic systems. PEOBS exhibits more than a fourfold enhancement in catalysis efficiency in comparison with a conventional biphasic system. Impressively, PEOBS enables the organic product to be facilely isolated through simple decantation and the nanoparticle catalyst can be recycled in situ without the need for “separation”. Its recycling effectiveness is justified by ten reaction cycles without significant catalyst loss. The simple protocol, in conjunction with the stability to simultaneously achieve high catalysis efficiency and excellent catalyst recyclability, makes PEOBS a promising methodology to develop more sustainable nanocatalysis.