A biosurfactant-assisted mechanical amorphous dispersion extraction (BA-MADE) procedure was established for the simultaneous capture of hydrophilic phenolic acids and hydrophobic tanshinones from Salvia miltiorrhiza. Single-factor experiments and the response surface methodology were used to optimize and analyze the crucial parameters for the method, such as the type and amount of amorphous-dispersion extractants, grinding time, extraction time and solid-to-liquid ratio. The optimized parameter values for the BA-MADE process were 407.02 mg of sodium chenodeoxycholate, a grinding time of 4.87 min, an extraction time of 4.92 min, and a solid-to-liquid ratio of 0.5:10 g/mL. The calibration curves of danshensu, rosmarinic acid, lithospermic acid, salvianolic acid B, salvianolic acid A, dihydrotanshinone I, cryptotanshinone, tanshinone I, and tanshinone II A exhibited good linearity in the range of 1–500 μg/mL (R2 ≥ 0.9990). The limits of detection of nine analytes ranged from 5.46 to 130 ng/mL, the relative standard deviations (RSDs) of intraday and interday precision were less than 1.95 and 3.56%, respectively, and the recoveries of the real sample were in the range of 85–113%, with RSD% below 3.21%. The BA-MADE method was compared with previously reported methods, such as heating reflux extraction, ultrasonic extraction and microwave-assisted micellar extraction, and the results demonstrated that the developed method has significant advantages in the simultaneous extraction of hydrophilic and hydrophobic active components from Salvia miltiorrhiza.