Charge a LiPo Battery Through VCC?
No.  Connecting a 3.7 V lithium cell to 5 V would damage the battery.

In electronics we have things called datasheets, which are provided by the manufacturer of devices to tell you exactly what these devices can do and what you must not do to them.  The datasheet for your battery should tell you how the battery can be charged.  You have to assume that anything outside of what the datasheet allows would be bad for the battery.  In the case of a lithium battery, exploding and causing your house to burn down are not out of the question.

GO READ THE DATASHEET.