To enhance the friction and wear properties of alloys, AlCrTiVNbx high-entropy alloys (HEAs) with various Nb contents were prepared using the arc melting technique and then annealed at 1000 °C for 2 h. The microstructure and hardness changes in the AlCrTiVNbx (x = 0.3, 0.4, and 0.5) HEAs after casting and annealing were studied via scanning electron microscopy, X-ray diffractometry, optical microscopy and the Vickers hardness test. The MFT-EC400 ball disc reciprocating friction and wear tester was used to investigate the wear resistance of the HEAs before and after annealing. The results show that the annealed AlCrTiVNbx HEAs changed from a single-phase structure to a multi-phase structure, and the content of the face-center cubic (FCC) phase and hexagonal close-packed (HCP) phase further increases with the increase in Nb content. The hardness value of the annealed HEAs is greatly enhanced compared with the casting state, and the hardness of the Nb0.5 HEA is increased from 543 HV to 725 HV after annealing. The wear resistance of the alloys after the annealing treatment is also greatly improved, among which Nb0.5 has the best wear resistance. The average friction coefficient of Nb0.5 is 0.154 and the wear rate is 2.117 × 10−5 mm3/(N·m). We believe that the precipitation strengthening after the annealing treatment and the lubrication effect of the FCC phase are the reasons for the significant improvement in wear resistance. The morphology of the samples indicates that the wear mechanism of the alloy includes adhesive wear, abrasive wear and a certain degree of oxidation wear.