To
increase the detection accuracy of radioactive samples, sample
preparation through liquid–liquid extraction (LLE) before instrumental
analysis is a crucial step. LLE preparation involves multiple steps
including the tedious separation steps of co-extraction and stripping,
which may cause sample loss, radioactive contamination, and radioactive
leaks. In this study, a novel hybrid slug flow–laminar flow
(SFLF) microchip in passive mode was designed to couple extraction
and stripping in situ to realize a one-step sample preparation. The
difficulty in maintaining stable water–organic–water
interfaces was mitigated by using a partition wall and three resistance
isolation areas. The mass transfer performance of the SFLF microchip
was investigated and compared with that of the supported liquid membrane
and three-layer laminar flow microextraction/stripping systems. Furthermore,
the applicability of the SFLF system in preparing radioactive samples
was validated through the selective separation of Ce and Pr from Cs
and Sr. The novel SFLF microextraction/stripping system has a stable
flow pattern, high mass transfer efficiency, and superior operating
flexibility.