Just consult the datasheet, it tells you everything you need to know, you shouldn't attempt to program a chip as complicated as the 16F877 without having the datasheet to hand.
As one of my old technical college teachers used to say "pin it up on the back of the toilet door, so you have plenty of time to study it" :lol:
Like what Nigel said, keep the datasheet on hand. Anyway to quickly get you answered:
VDD - connect to 5V the two pins marked VDD. This is used to power the chip. Why two? To reduce the inductance of the wires supplying the chip and minimize minute voltage drops as a result of rapid changes in current being drawn by the chip. This ensures stable operation of the chip.
VSS - connect to 0V or GND the two pins marked VSS.
MCLR - This pin when brought to 0V, resets the PIC. This pin also doubles as a VPP pin. When the pin raised to 8.5V-13.5V, the PIC is changed into programming mode. This pin is normally connected to VDD thru a resistor for normal use.