Galileo can independently provide navigation and positioning services globally. Galileo satellites transmit quad-frequency E1, E5a, E5b, and E5 signals, which can benefit the integer ambiguity rapid resolution. Firstly, the qualities of Galileo signals from Carrier-to-Noise (C/N0), Multipath Combination (MPC), and pseudo-range and phase noise using the ultra-short baseline were evaluated. The experimental results indicated that the Galileo E5 signal has the highest C/N0, while the C/N0 of other signals is lower and almost equal. In terms of MPC, the Galileo E1 was the most severe followed by E5a and E5b, and the MPC of E5 is less severe. As for the precision of un-differenced observations, the carrier phase and pseudo-range observations of Galileo E5 had higher accuracy than those of Galileo E5a, E5b, and E1. Secondly, the quad-frequency observations allowed for various linear combinations of different frequencies, which provides some feasibility for improving the performance of ambiguity resolution. Assuming that the phase noise and the first-order ionosphere , the total noise of the Extra-Wide-Lane (EWL) combination observation ((0, 0, 1, −1) and (0, −1, 1, 0)) and Very-Wide-Lane (VWL) combination observation ((0, −2, 1, 1), (0, −3, 2, 1)) are still less than 0.5 cycles. Finally, a geometry-based quad-frequency carrier ambiguities (GB-QCAR) method was developed, and all different options of linear combinations were investigated systematically from the ambiguity-fixed rate with two baselines. Experimental results demonstrated that, the ambiguity fixed rate of combination observation (0, −1, 1, 0), (0, −3, 5, −2), (1, −1, 0, 0) and (0, 0, 0, 1) is the highest and the positioning accuracy of VWL combination observation (0, −3, 5, −2) is equivalent to that of the EWL combination observation (0, −1, 1, 0). The positioning accuracies of WL combination observation (1, −1, 0, 0) are preferable to 3 cm and 10 cm in the horizontal and vertical, respectively. The positioning accuracy of NL combination observation E5 in the horizontal direction is about 1 cm, and is better than 4 cm in the vertical direction. Therefore, we can use Galileo observations to realize high-precise navigation services utilizing the proposed GB-QCAR method.